U.S. patent application number 15/039690 was filed with the patent office on 2016-12-29 for composition for low temperature.
This patent application is currently assigned to BASF SE. The applicant listed for this patent is BASF SE. Invention is credited to DIRK RETTEMEYER, Ronny RINKLIEB, Markus SHERER.
Application Number | 20160376518 15/039690 |
Document ID | / |
Family ID | 49667064 |
Filed Date | 2016-12-29 |
United States Patent
Application |
20160376518 |
Kind Code |
A1 |
RETTEMEYER; DIRK ; et
al. |
December 29, 2016 |
COMPOSITION FOR LOW TEMPERATURE
Abstract
Lubricant composition comprising a dicarboxylic acid ester
component which is formed from a dicarboxylic acid selected from
the list consisting of adipic acid, phthalic acid, pimilic acid,
suberic acid, azelaic acid and sebacic acid, and mixtures thereof
and a branched aliphatic alcohol R--OH which is defined according
to the following formula (I) ##STR00001## whereas q, r and s are
defined as follows, q+r=4 to 9, s=0 to 5, q=1 to 8, and r=1 to 6,
and an ethylene-propylene copolymer.
Inventors: |
RETTEMEYER; DIRK;
(Hueckelhoven, DE) ; RINKLIEB; Ronny; (Dusseldorf,
DE) ; SHERER; Markus; (Mannheim, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BASF SE |
Ludwigshafen |
|
DE |
|
|
Assignee: |
BASF SE
Ludwigshafen
DE
|
Family ID: |
49667064 |
Appl. No.: |
15/039690 |
Filed: |
November 27, 2014 |
PCT Filed: |
November 27, 2014 |
PCT NO: |
PCT/EP2014/075816 |
371 Date: |
May 26, 2016 |
Current U.S.
Class: |
508/499 |
Current CPC
Class: |
C10M 105/36 20130101;
C10M 2207/282 20130101; C10N 2040/04 20130101; C10N 2030/68
20200501; C10M 2207/30 20130101; C10M 2205/022 20130101; C10M
2207/2825 20130101; C10M 2205/024 20130101; C10N 2040/08 20130101;
C10N 2040/25 20130101; C10M 2205/028 20130101; C10M 111/04
20130101; C10N 2030/02 20130101; C10M 2207/281 20130101; C10M
2205/0245 20130101; C10N 2030/10 20130101; C10N 2020/02 20130101;
C10M 2205/0285 20130101; C10N 2040/02 20130101; C10N 2040/135
20200501; C10N 2040/30 20130101; C10M 169/041 20130101; C10M
2205/0225 20130101; C10M 2205/022 20130101; C10M 2205/024 20130101;
C10M 2205/0225 20130101; C10M 2205/0245 20130101 |
International
Class: |
C10M 111/04 20060101
C10M111/04; C10M 169/04 20060101 C10M169/04 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 28, 2013 |
EP |
13194911.7 |
Claims
1.-10. (canceled)
11. A lubricant composition comprising based on the total weight of
the lubricant composition a) 35 to 95 wt.-% of a dicarboxylic acid
ester component which is selected from diisononyladipate (DNA) and
di-(2-ethylhexyl)adipate (DOA), b) 5 to 30 wt.-% of an
ethylene-propylene copolymer, and c) 5 to 25 wt.-% of a
monocarboxylic acid ester.
12. The lubricant composition according to claim 11, wherein the
lubricant composition has a kinematic viscosity according to
industrial standard DIN 51562-1 of not more than 1600 mm.sup.2/s at
-30.degree. C. and of at least 7.5 mm.sup.2/s at 100.degree. C.
13. The lubricant composition according to claim 11, having a
viscosity index according to the industrial standard DIN ISO 2909
of at least 160.
14. The lubricant composition according to claim 11, wherein the
dicarboxylic acid ester has a kinematic viscosity according to DIN
51562-1 in the range of 2 to 15 mm.sup.2/s at 100.degree. C.
15. The lubricant composition according to claim 11, wherein the
ethylene-propylene copolymer has a kinematic viscosity according to
JIS K 2283 at 100.degree. C. in the range of from 1000 to 2200
mm.sup.2/s.
16. The lubricant composition according to claim 11, further
comprising a base oil component having a kinematic viscosity
according to DIN 51562-1 at 100.degree. C. in the range of from 1
to 5 mm.sup.2/s.
17. The lubricant composition according to claim 11, wherein the
monocarboxylic acid ester is selected from the list consisting of
2-ethylhexyloleate, 2-ethylhexylcocoate, 2-ethylhexylpalmitate,
2-ethylhexylstearate, 2-ethylhexyltallowate, and mixtures
thereof.
18. The lubricant composition according to claim 11, wherein the
ratio of the dicarboxylic acid ester component to the oligomeric
copolymers in the lubricant compositions according to the present
invention is in the range of from 2:1 to 19:1 based on the relative
weight of these components in the lubricant compositions according
to the present invention.
19. The lubricant composition according to claim 11, further
comprising an additive component which is present in an amount of
0.1 to 20 wt % of the total lubricant composition.
20. A vehicle transmission oil, axle oil, industrial transmission
oil, industrial gear oil, compressor oil, turbine oil, hydraulic
oil or motor oil which comprises the lubricant composition
according to claim 11.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a national stage application (under 35
U.S.C. .sctn.371) of PCT/EP2014/075816, filed Nov. 27, 2014, which
claims benefit of European Application No. 13194911.7, filed Nov.
28, 2013, both of which are incorporated herein by reference in
their entirety.
DESCRIPTION
[0002] The present invention relates to the field of lubricants.
The lubricant compositions contain a di-carboxylic acid ester and
an ethylene-propylene copolymer. The lubricant compositions can be
used in a variety of different oil formulations required in motor
vehicles.
TECHNICAL BACKGROUND
[0003] Commercially available lubricant compositions are based on a
multitude of different natural or synthetic components. The
resulting properties of the various existing lubricant compositions
are tailored to the specific technical requirements by the addition
of further components and selected combinations thereof. In this
way, lubricant compositions are obtained which can fulfill the
complex requirements associated with the various special technical
applications in the field of motor vehicles, automotive engines and
other machinery.
[0004] Typically, lubricant compositions are needed that provide
high shear stability, improved low-temperature viscosity, minimum
degree of evaporation loss, good fuel efficiency, acceptable seal
compatibility and excellent wear protection.
[0005] One especially desired set of properties in high performance
lubrication applications is an excellent low temperature profile
indicated by favorable low temperature viscosity in combination
with excellent dynamic behavior at high temperatures as indicated
by high shear stability and high viscosity index.
[0006] Known lubricants which are able to fulfill such performance
characteristics have been developed in the prior art by the
addition of special thickening agents (viscosity index improving
agents). Preferably, polyalphaolefin (PAO)-type base components
have been modified with thickeners like polyisobutenes (PIB),
oligomeric co-polymers (OCPs), polymethacrylates (PMAs) or high
viscosity esters (complex esters) for achieving the desired set of
properties.
[0007] U.S. Pat. No. 5,451,630 describes the general dilemma when
using thickening agents in lubricant compositions because the
increase of viscosity is directly related to the molecular weight
of the polymeric thickening agent while on the other hand the shear
stability decreases due to the greater tendency of breakage under
shear and high temperature conditions.
[0008] U.S. Pat. No. 5,451,630 further suggests oligomeric
copolymers which are demonstrated to provide good shear stability
to lubricant compositions.
[0009] In WO 2007/144079 A2, a larger number of lubricant
compositions have been described including a variety of different
thickening agents like PIBs, OCPs, PMAs and high viscosity esters
which have been demonstrated to be generally applicable as
viscosity index improvers.
[0010] In addition, dicarboxylic acid esters like DIDA (diisodecyl
adipate), DITA (diisotridecyl adipate) or TMTC (trimethylolpropane
caprylate) have also been added to such lubricant compositions as
solubilizers for polar additive types.
[0011] However, there is a continued need for new lubricant
compositions which exceed the performance characteristics of the
already existing lubricant compositions. This is particularly
important for lubricant compositions that are designed for the use
under extreme conditions. It is particularly difficult to develop
lubricant compositions that offer the desired excellent rheological
properties at very low temperatures as well as at elevated
temperatures.
[0012] Surprisingly, lubricant compositions are provided by the
present invention comprising the combination of a dicarboxylic acid
ester component with an ethylene-propylene copolymer having
excellent dynamic behavior at high temperature and unusual high
viscosity index while the corresponding viscosity at very low
temperatures still remains only moderate. Another important
property is the high permanent shear stability of the lubricant
compositions according to the present invention.
DESCRIPTION OF THE INVENTION
[0013] The present invention relates to a lubricant composition
comprising [0014] a) a dicarboxylic acid ester component which is
formed from a dicarboxylic acid selected from the list consisting
of adipic acid, phthalic acid, pimilic acid, suberic acid, azelaic
acid and sebacic acid, and mixtures thereof and a branched
aliphatic alcohol R--OH which is defined according to the following
formula (I)
[0014] ##STR00002## [0015] whereas q, r and s are defined as
follows, [0016] q+r=4 to 9, [0017] s=0 to 5, [0018] q=1 to 8, and
[0019] r=1 to 6, [0020] and [0021] b) an ethylene-propylene
copolymer.
[0022] In another preferred embodiment, in the lubricant
composition from above, the residue R in the branched aliphatic
alcohol R--OH is selected from ethylhexyl, methyloctyl,
propylheptyl, butyloctyl and mixtures thereof whereas q, r and s
are defined as follows
TABLE-US-00001 R in R--OH Ethylhexyl q + r = 4 s = 1 q = 1 r = 3 q
= 2 r = 2 q = 3 r = 1 Methyloctyl q + r = 6 s = 0 q = 1 r = 5 q = 2
r = 4 q = 3 r = 3 q = 4 r = 2 q = 5 r = 1 Propylheptyl q + r = 5 s
= 2 q = 1 r = 4 q = 2 r = 3 q = 3 r = 2 q = 4 r = 1 Butyloctyl q +
r = 6 s = 3 q = 1 r = 5 q = 2 r = 4 q = 3 r = 3 q = 4 r = 2 q = 5 r
= 1
[0023] In another preferred embodiment, the residue R in the
branched aliphatic alcohol R--OH from above according to formula
(I)
##STR00003##
[0024] is defined by q, r and s as follows, [0025] q+r=4 to 9,
[0026] s=0 to 5, [0027] q=3 to 8, and [0028] r=1.
[0029] In another preferred embodiment, the lubricant compositions
as defined above additionally have a kinematic viscosity according
to industrial standard DIN 51562-1 of not more than 1600 mm.sup.2/s
at -30.degree. C. and of at least 7.5 mm.sup.2/s at 100.degree.
C.
[0030] In another preferred embodiment, the lubricant composition
comprises [0031] a) a dicarboxylic acid ester component [0032] b)
an ethylene-propylene copolymer, wherein the lubricant composition
has a kinematic viscosity according to industrial standard DIN
51562-1 of not more than 1600 mm.sup.2/s at -30.degree. C. and of
at least 7.5 mm.sup.2/s at 100.degree. C.
[0033] In another preferred embodiment, the lubricant composition
has a viscosity index according to the industrial standard DIN ISO
2909 of at least 160, preferably of at least 180.
[0034] In another preferred embodiment, the dicarboxylic acid ester
has a kinematic viscosity according to DIN 51562-1 in the range of
from 2 to 15 mm.sup.2/s at 100.degree. C.
[0035] In another preferred embodiment, the dicarboxylic acid ester
is selected from the list consisting of di-(2-propylheptyl)adipate
(DPHA), di-isononyladipate (DNA), di-(2-ethylhexyl)adipate (DOA),
dipropylheptylphthalate (DPHP) and mixtures thereof.
[0036] In another preferred embodiment, the ethylene-propylene
copolymer has a kinematic viscosity according to ASTM D445 at
100.degree. C. in the range of from 1000 to 2200 mm.sup.2/s.
[0037] In another preferred embodiment, the lubricant composition
further comprises a base oil component having a kinematic viscosity
according to DIN 51562-1 of from about 1 to 5 mm.sup.2/s at
100.degree. C., preferably a PAO-2 component.
[0038] In another preferred embodiment, the lubricant composition
further comprises a monocarboxylic acid ester.
[0039] In another preferred embodiment, the monocarboxylic acid
ester is selected from the list consisting of 2-ethylhexyloleate,
2-ethylhexylcocoate, 2-ethylhexylpalmitate, 2-ethylhexylstearate,
and 2-ethylhexyltallowate, and mixtures thereof.
[0040] In another preferred embodiment, the ratio of the
dicarboxylic acid ester component to the oligomeric copolymers in
the lubricant compositions according to the present invention is in
the range of from 2:1 to 19:1, preferably 3:1 to 10:1 based on the
relative weight of these components in the lubricant compositions
according to the present invention.
[0041] In another preferred embodiment, the lubricant composition
further comprises an additive component which is present in an
amount of 0.1 to 20 wt % of the total lubricant composition.
[0042] In another preferred embodiment, the lubricant compositions
are used as vehicle transmission oil, axle oil, industrial
transmission oil, compressor oil, turbine oil, hydraulic oil or
motor oil.
[0043] The lubricant composition according to the present invention
comprises [0044] a) a dicarboxylic acid ester component which is
formed from a dicarboxylic acid selected from the list consisting
of adipic acid, phthalic acid, pimilic acid, suberic acid, azelaic
acid and sebacic acid and mixtures thereof, and a branched
aliphatic alcohol R--OH which is defined according to the following
formula (I)
[0044] ##STR00004## [0045] whereas q, r and s are defined as
follows, [0046] q+r=4 to 9, [0047] s=0 to 5, [0048] q=1 to 8, and
[0049] r=1 to 6, [0050] and [0051] b) an ethylene-propylene
copolymer.
[0052] Preferably, the branched aliphatic alcohol R--OH according
to formula (I) can be a primary C.sub.7 to C.sub.12 alcohol,
wherein the alkyl side chain is C.sub.1 to C.sub.6 alkyl (s=0 to
5). The alkyl side chain can be linear or branched alkyl group
while linear alkyl group is preferred for the alkyl side chain.
[0053] Accordingly, the main alkyl chain in residue R is C.sub.6 to
C.sub.11. Accordingly, the residue R in R--OH of formula (I)
includes methylhexyl, ethylhexyl, propylhexyl, butylhexyl,
pentylhexyl and hexylhexyl, methylheptyl, ethylheptyl,
propylheptyl, butylheptyl and pentylheptyl, methyloctyl,
ethyloctyl, propyloctyl, and butyloctyl, methylnonyl, ethylnonyl,
and propylnonyl, methyldecyl and ethyldecyl, and methylundecyl.
[0054] Especially preferred alcohols R--OH from the above list
include residue R being ethylhexyl, methyloctyl, propylheptyl and
butyloctyl.
[0055] Most preferably, the residue R in R--OH in the above
lubricant composition is selected from ethylhexyl, methyloctyl,
propylheptyl, butyloctyl and mixtures thereof defined by q, r and s
as follows
TABLE-US-00002 R in R--OH Ethylhexyl q + r = 4 s = 1 q = 1 r = 3 q
= 2 r = 2 q = 3 r = 1 Methyloctyl q + r = 6 s = 0 q = 1 r = 5 q = 2
r = 4 q = 3 r = 3 q = 4 r = 2 q = 5 r = 1 Propylheptyl q + r = 5 s
= 2 q = 1 r = 4 q = 2 r = 3 q = 3 r = 2 q = 4 r = 1 Butyloctyl q +
r = 6 s = 3 q = 1 r = 5 q = 2 r = 4 q = 3 r = 3 q = 4 r = 2 q = 5 r
= 1
[0056] Especially preferred are the alcohols having q+r=4 to 9, r=1
and q=3 to 8, i.e. the primary aliphatic C.sub.7 to C.sub.12
alcohols in which the linear (which is preferred) or branched alkyl
side chain C.sub.1 to C.sub.6 alkyl (s=0 to 5) is located at the
2-position of the primary alcohol. Such alcohols are typically
named Guerbet alcohols as further explained below.
[0057] It is additionally preferred that the kinematic viscosity of
the lubricant compositions from above based on the industrial
standard DIN 51562-1 at a temperature of -30.degree. C. is not
higher than 1600 mm.sup.2/s, preferably not higher than 1550
mm.sup.2/s, and even not higher than 1500 mm.sup.2/s, and/or,
preferably, the kinematic viscosity based on the industrial
standard DIN 51562-1 at a temperature of 100.degree. C. is at least
7.0 mm.sup.2/s, preferably at least 7.5 mm.sup.2/s, and even more
preferably at least 8.0 mm.sup.2/s.
[0058] From a rheological perspective, the kinematic viscosity of
the lubricant compositions according to the present invention based
on the industrial standard DIN 51562-1 at a temperature of
-30.degree. C. is, in its most generic definition, not higher than
1600 mm.sup.2/s, preferably not higher than 1550 mm.sup.2/s, and
even not higher than 1500 mm.sup.2/s, even more preferably not
higher than 1400 mm.sup.2/s and most preferably not higher than
1300 mm.sup.2/s. The kinematic viscosity of the lubricant
compositions according to the present invention based on the
industrial standard DIN 51562-1 at a temperature of -30.degree. C.
is at least 500 mm.sup.2/s, more preferably at least 700
mm.sup.2/s, and even more preferably at least 900 mm.sup.2/s.
[0059] That is, the lubricant composition according to the present
invention, when most generically defined, comprises a) a
dicarboxylic acid ester component and b) an ethylene-propylene
copolymer, while the resulting kinematic viscosity of the lubricant
composition based on the industrial standard DIN 51562-1 at a
temperature of -30.degree. C. is, in its most generic definition,
not higher than 1600 mm.sup.2/s, preferably not higher than 1550
mm.sup.2/s, and even not higher than 1500 mm.sup.2/s.
[0060] The kinematic viscosity based on the industrial standard DIN
51562-1 at a temperature of 40.degree. C. is at least 25
mm.sup.2/s, preferably at least 30 mm.sup.2/s, and even more
preferably at least 35 mm.sup.2/s.
[0061] The kinematic viscosity based on the industrial standard DIN
51562-1 at a temperature of 100.degree. C. is at least 7.0
mm.sup.2/s, preferably at least 7.5 mm.sup.2/s, and even more
preferably at least 8.0 mm.sup.2/s.
[0062] The rheological profile of the lubricant compositions
according to the present invention is especially defined by a
kinematic viscosity based on the industrial standard DIN 51562-1 a
temperature of -30.degree. C. which is not higher than 1600
mm.sup.2/s, preferably not higher than 1550 mm.sup.2/s, and even
more preferably not higher than 1500 mm.sup.2/s and a kinematic
viscosity based on the industrial standard DIN 51562-1 at a
temperature of 100.degree. C. which is at least 7.0 mm.sup.2/s,
preferably at least 7.5 mm.sup.2/s, and even more preferably at
least 8.0 mm.sup.2/s.
[0063] Further, the rheological profile of the lubricant
compositions according to the present invention is characterized by
a viscosity index based on the industrial standard DIN ISO 2909 of
at least 160, more preferably of at least 190, and even more
preferably of at least 200.
[0064] The lubricant compositions according to the present
invention have a pour point according to DIN ISO 3016 of not higher
than -50.degree. C., preferably not higher than -60.degree. C., and
even more preferably not higher than -70.degree. C.
[0065] Preferably, the lubricant compositions according to the
present invention have a kinematic viscosity based on the
industrial standard DIN 51562-1 at a temperature of -30.degree. C.
which is not higher than 1600 mm.sup.2/s, preferably not higher
than 1550 mm.sup.2/s, and even not higher than 1500 mm.sup.2/s, and
a kinematic viscosity based on the industrial standard DIN 51562-1
at a temperature of 100.degree. C. which is at least 7.0
mm.sup.2/s, preferably at least 7.5 mm.sup.2/s, and even more
preferably at least 8.0 mm.sup.2/s, and a viscosity index based on
the industrial standard DIN ISO 2909 of at least 160, more
preferably of at least 180, and even more preferably of at least
200.
[0066] The lubricant compositions according to the present
invention include the following components which are described
below in more detail.
[0067] The lubricant compositions according to the present
invention include as the first essential component a dicarboxylic
acid ester component.
[0068] In its most generic definition as understood in the present
invention, the dicarboxylic ester component as used in the
lubricant compositions according to the present invention is
defined as a dicarboxylic ester component having kinematic
viscosity at 100.degree. C. (DIN 51562-1) in the range of 2 to 15
mm.sup.2/s, preferably 3 to 10 mm.sup.2/s, or even more preferably
4 to 8 mm.sup.2/s.
[0069] The dicarboxylic ester component has a pour point (DIN ISO
3016) in the range of from -20.degree. C. to -75.degree. C.,
preferably in the range of from -40.degree. C. to -60.degree. C.
and most preferably in the range of from -48.degree. C. to
-60.degree. C.
[0070] The viscosity index (DIN ISO 2909) of the dicarboxylic ester
component is in the range of from 120 to 170, preferably of from
130 to 160, and most preferably of from 135 to 145.
[0071] The kinematic viscosity of the dicarboxylic ester component
at 40.degree. C. (DIN 51562-1) is in the range of 7 to 50
mm.sup.2/s, preferably 10 to 30 mm.sup.2/s, and most preferably 12
to 28 mm.sup.2/s.
[0072] The amount of the dicarboxylic acid ester component in the
lubricant compositions according to the present invention is in the
range of from 35 to 95 wt %, preferably in the range of from 55 to
85 wt %, and even more preferably in the range of from 65 to 80 wt
% based on the total weight of the lubricant composition.
[0073] The dicarboxylic ester preferably is derived from the
reaction of a dicarboxylic acid with an aliphatic alcohol.
[0074] Preferred dicarboxylic acids are adipic acid, pimelic acid,
suberic acid, azelaic acid and sebacic acid and mixtures thereof.
The dicarboxylic acid ester component is preferably formed from
such dicarboxylic acids by esterification with medium-size
aliphatic alcohols, which can be linear or branched, preferably
C.sub.5 to C.sub.20 alcohol, more preferably C.sub.9 to C.sub.15
aliphatic alcohol and most preferably nonanol, isodecanol,
isotridecanol and 2-propyl heptanol.
[0075] Another preferred group of alcohols is derived from
so-called Guerbet alcohols or mixtures thereof. The trivial name of
Guerbet alcohol is used for 2-alkyl-substituted 1-alkanols whose
industrial synthesis is described inter alia in H. Machemer,
Angewandte Chemie, Vol. 64, pages 213-220 (1952) and in G.
Dieckelmann and H. J. Heinz in "The Basics of Industrial
Oleochemistry", pages 145-145 (1988). In one preferred embodiment
the Guerbet alcohol is derived at least partly from 2-hexyl
decanol, 2-hexyl dodecanol, 2-octyl decanol and/or 2-octyl
dodecanol.
[0076] Alternatively, the dicarboxylic acid ester component can be
a trimethylolpropane-type ester, preferably formed with
C.sub.8-C.sub.10 aliphatic alcohol, e.g. trimethylolpropane
caprylate (TMTC), which is commercially available as Synative ES
TMTC.RTM. (from BASF SE).
[0077] An additionally preferred dicarboxylic ester component is
diisotridecyl adipate (DITA). Such ester is for example
commercially available under the trademark Synative ES DIDA.RTM.
from BASF SE.
[0078] The dicarboxylic acid ester may include one of the following
four particularly preferred embodiments.
[0079] In a first particularly preferred embodiment, the
dicarboxylic ester component according to the present invention is
obtainable by reacting a mixture comprising [0080] a) at least one
acid selected from the group consisting of aliphatic dicarboxylic
acids and aliphatic dicarboxylic acid anhydrides, [0081] b1) a
monoalcohol having 10 carbon atoms and a structure of the general
formula I,
[0081] ##STR00005## [0082] wherein [0083] R.sub.1 is selected from
the group consisting of pentyl, iso-pentyl, 2-methyl-butyl,
3-methyl-butyl and 2,2-dimethyl-propyl, [0084] R.sub.2 is H or
methyl, [0085] R.sub.3 is selected from the group consisting of
ethyl, propyl and iso-propyl, and [0086] b2) a monoalcohol having
10 carbon atoms and a structure of the general formula II,
[0086] ##STR00006## [0087] wherein [0088] R.sub.4 is selected from
the group consisting of pentyl, iso-pentyl, 2-methyl-butyl,
3-methyl-butyl and 2,2-dimethyl-propyl, [0089] R.sub.5 is H or
methyl, [0090] R.sub.6 is selected from the group consisting of
ethyl, propyl and iso-propyl, with the proviso that the monoalcohol
b1) and the monoalcohol b2) have a different structure.
[0091] Preferably, the aliphatic dicarboxylic acid is selected from
the group consisting of glutaric acid, diglycolic acid, succinic
acid, azelaic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid,
adipic acid, 2,6-decahydronaphthalenedicarboxylic acid,
1,3-cyclohexanedicarboxylic acid, and 2,5-norbornanedicarboxylic
acid. More preferably, the aliphatic dicarboxylic acid is adipic
acid.
[0092] The acids can be used either in pure form or in the form of
mixtures with monocarboxylic acids. Instead of the acids, their
anhydrides can also be used. Representative monocarboxylic acids
include n-butanoic acid, n-pentanoic acid, n-hexanoic acid,
n-heptanoic acid, n-octanoic acid, n-nonanoic acid, n-decanoic
acid, isobutanoic acid, isopentanoic acid, isohexanoic acid,
isoheptanoic acid, isooctanoic acid, 2-ethylhexanoic acid,
isononanoic acid, 3,5,5-trimethylhexanoic acid, and isodecanoic
acid.
[0093] Preferably the monoalcohol b1) is selected from the group
consisting of 2-propylheptanol, 2-propyl-4-methyl-hexanol,
2-propyl-5-methyl-hexanol, 2-isopropyl-4-methyl-hexanol,
2-isopropyl-5-methyl-hexanol, 2-propyl-4,4-dimethylpentanol,
2-ethyl-2,4-dimethylhexanol, 2-ethyl-2-methyl-heptanol,
2-ethyl-2,5-dimethylhexanol and 2-isopropyl-heptanol. More
preferably the monoalcohol b1) is 2-propyl-heptanol.
[0094] Preferably the monoalcohol b2) is selected from the group
consisting of 2-propylheptanol, 2-propyl-4-methyl-hexanol,
2-propyl-5-methyl-hexanol, 2-isopropyl-4-methyl-hexanol,
2-isopropyl-5-methyl-hexanol, 2-propyl-4,4-dimethylpentanol,
2-ethyl-2,4-dimethylhexanol, 2-ethyl-2-methyl-heptanol,
2-ethyl-2,5-dimethylhexanol and 2-isopropyl-heptanol. More
preferably the monoalcohol b2) is 2-propyl-4-methyl-hexanol.
[0095] Preferably the weight ratio of monoalcohol b1) to
monoalcohol b2) is in the range of 5:1 to 95:1, more preferably in
the range of 6:1 to 50:1, even more preferably in the range of 10:1
to 40:1, most preferably in the range of 20:1 to 35:1.
[0096] Preferably the mixture further comprises a monoalcohol b3)
having 10 carbon atoms and a structure of the general formula
III,
##STR00007##
wherein [0097] R.sub.7 is selected from the group consisting of
pentyl, iso-pentyl, 2-methyl-butyl, 3-methyl-butyl and
2,2-dimethyl-propyl, [0098] R.sub.8 is H or methyl, [0099] R.sub.9
is selected from the group consisting of ethyl, propyl and
iso-propyl, with the proviso that monoalcohol b3) has a different
structure from both the monoalcohol b1) and the monoalcohol
b2).
[0100] Preferably the monoalcohol b3) is selected from the group
consisting of 2-propylheptanol, 2-propyl-4-methyl-hexanol,
2-propyl-5-methyl-hexanol, 2-isopropyl-4-methyl-hexanol,
2-isopropyl-5-methyl-hexanol, 2-propyl-4,4-dimethylpentanol,
2-ethyl-2,4-dimethylhexanol, 2-ethyl-2-methyl-heptanol,
2-ethyl-2,5-dimethylhexanol and 2-isopropyl-heptanol. More
preferably the monoalcohol b3) is 2-propyl-5-methyl-hexanol.
[0101] Preferably the mixture comprises 80 to 95 weight-% of
2-n-propyl-heptanol as component b1), 1.0 to 10 weight. % of
2-propyl-4-methyl-hexanol as component b2), 1.0 to 10 weight-% of
2-propyl-5-methyl-hexanol as component b3) and 0.1 to 2.0 weight-%
of 2-isopropyl-heptanol, whereby the weight of each component is
related to the total weight of the monoalcohols. More preferably
the mixture comprises 91.0 to 95.0 weight-% of 2-n-propyl-heptanol
as component b1), 2.0 to 5.0 weight-% of 2-propyl-4-methyl-hexanol
as component b2), 3.0 to 5.0 weight-% of 2-propyl-5-methyl-hexanol
as component b3) and 0.1 to 0.8 weight-% of 2-isopropyl-heptanol,
whereby the weight of each component is related to the total weight
of the monoalcohols.
[0102] The dicarboxylic ester component according to the present
invention also includes dicarboxylic acid esters which are obtained
by reacting a mixture comprising adipic acid, 2-propyl-heptanol,
2-propyl-4-methyl-hexanol and 2-propyl-5-methyl-hexanol.
[0103] The dicarboxylic ester component according to the present
invention further includes dicarboxylic acid esters which are
obtained by reacting a mixture comprising adipic acid and 80 to 95
weight-% of 2-n-propyl-heptanol, 1.0 to 10 weight. % of
2-propyl-4-methyl-hexanol, 1.0 to 10 weight-% of
2-propyl-5-methyl-hexanol and 0.1 to 2.0 weight-% of
2-isopropyl-heptanol, whereby the weight of each component is
related to the total weight of the monoalcohols.
[0104] The most preferred dicarboxylic acid ester according to the
first particularly preferred embodiment is
di-(2-propylheptyl)-adipate (DPHA). This compound also is
commercially available as DPHA-XPB 115 (BASF SE).
[0105] In a second particularly preferred embodiment, the
dicarboxylic ester component according to the present invention is
diisononyl adipate (DNA).
[0106] The diisononyl adipate (DNA) is obtainable by reacting a
mixture comprising adipic acid and an alcohol mixture comprising
1-nonanol, monomethyloctanols, dimethylheptanols and
monoethylheptanols whereby the polyester has a viscosity at
40.degree. C. in the range of 5 to 15 mm.sup.2/s determined
according to DIN 51562-1. The viscosity of the polyester at
40.degree. C. is preferably from 6 to 14 mm.sup.2/s, more
preferably from 7 to 13 mm.sup.2/s, and most preferably from 8 to
12 mm.sup.2/s determined according to DIN 51562-1.
[0107] The polyesters prepared by reacting a mixture comprising
adipic acid and an alcohol mixture comprising 1-nonanol,
monomethyloctanols, dimethylheptanols and monoethylheptanols
preferably have a density at 20.degree. C. according to DIN 51757
of from 0.85 to 1.00 g/cm.sup.3, more preferably from 0.88 to 0.95
g/cm.sup.3 and most preferably from 0.90 to 0.94 g/cm.sup.3. The
refractive index n.sub.D.sup.20 according to DIN 51423 is
preferably from 1.400 to 1.500, more preferably from 1.420 to
1.480, and most preferably from 1.440 to 1.460.
[0108] The alcohol mixture comprising 1-nonanol,
monomethyloctanols, dimethylheptanols and monoethylheptanols is
particularly advantageously obtainable in a process involving two
or more stages and starting from a hydrocarbon mixture comprising
butenes. In a first step, the butenes are dimerized to give a
mixture of isomeric octenes. The octene mixture is then
hydroformylated to give C.sub.9 aldehydes and then hydrogenated to
give the alcohol mixture. In this reaction sequence, specific,
defined parameters have to be adhered to, at least during the
butene dimerization, preferably during the butene dimerization and
the hydroformylation.
[0109] It is preferable, therefore, that the isomeric octenes
mixture is obtained by bringing a hydrocarbon mixture comprising
butenes into contact with a heterogeneous catalyst comprising
nickel oxide. The isobutene content of the hydrocarbon mixture is
preferably 5% by weight or less, in particular 3% by weight or
less, particularly preferably 2% by weight or less, and most
preferably 1.5% by weight or less, based in each case on the total
butene content. A suitable hydrocarbon stream is that known as the
C.sub.4 cut, a mixture of butenes and butanes, available in large
quantities from FCC plants or from steam crackers. A starting
material used with particular preference is that known as raffinate
II, which is an isobutene-depleted C.sub.4 cut.
[0110] A preferred starting material comprises from 50 to 100% by
weight, preferably from 80 to 95% by weight, of butenes and from 0
to 50% by weight, preferably from 5 to 20% by weight, of butanes.
The following makeup of the butenes can be given as a general guide
to quantities:
TABLE-US-00003 1-butene from 1 to 98% by weight, cis-2-butene from
1 to 50% by weight, trans-2-butene from 1 to 98% by weight, and
isobutene up to 5% by weight.
[0111] Possible catalysts are catalysts known per se and comprising
nickel oxide, as described, for example, by O'Connor et al. in
Catalysis Today, 6, (1990) p. 329. Supported nickel oxide catalysts
may be used, and possible support materials are silica, alumina,
aluminosilicates, aluminosilicates having a layer structure and
zeolites. Particularly suitable catalysts are precipitation
catalysts obtainable by mixing aqueous solutions of nickel salts
and of silicates, e.g. of sodium silicate and sodium nitrate, and,
where appropriate, of other constituents, such as aluminum salts,
e. g. aluminum nitrate, and calcining.
[0112] Particular preference is given to catalysts which
essentially consist of NiO, SiO.sub.2, TiO.sub.2 and/or ZrO.sub.2,
and also, where appropriate, Al.sub.2O.sub.3. A most preferred
catalyst comprises, as significant active constituents, from 10 to
70% by weight of nickel oxide, from 5 to 30% by weight of titanium
dioxide and/or zirconium dioxide and from 0 to 20% by weight of
aluminum oxide, the remainder being silicon dioxide. A catalyst of
this type is obtainable by precipitating the catalyst composition
at pH from 5 to 9 by adding an aqueous solution comprising nickel
nitrate to an aqueous alkali metal water glass solution which
comprises titanium dioxide and/or zirconium dioxide, filtering,
drying and annealing at from 350 to 650.degree. C. For details of
preparation of these catalysts reference may be made to DE-A
4339713. The entire content of the disclosure of that publication
is incorporated herein by way of reference.
[0113] The hydrocarbon mixture comprising butenes is brought into
contact with the catalyst, preferably at temperatures of from 30 to
280.degree. C., in particular from 30 to 140.degree. C. and
particularly preferably from 40 to 130.degree. C. This preferably
takes place at a pressure of from 10 to 300 bar, in particular from
15 to 100 bar and particularly preferably from 20 to 80 bar. The
pressure here is usefully set in such a way that the olefin-rich
hydrocarbon mixture is liquid or in the supercritical state at the
temperature selected.
[0114] Examples of reactors suitable for bringing the hydrocarbon
mixture into contact with the heterogeneous catalyst are
tube-bundle reactors and shaft furnaces. Shaft furnaces are
preferred because the capital expenditure costs are lower. The
dimerization may be carried out in a single reactor, where the
oligomerization catalyst may have been arranged in one or more
fixed beds.
[0115] Another way is to use a reactor cascade composed of two or
more, preferably two, reactors arranged in series, where the butene
dimerization in the reaction mixture is driven to only partial
conversion on passing through the reactor(s) preceding the last
reactor of the cascade, and the desired final conversion is not
achieved until the reaction mixture passes through the last reactor
of the cascade. The butene dimerization preferably takes place in
an adiabatic reactor or in an adiabatic reactor cascade.
[0116] After leaving the reactor or, respectively, the last reactor
of a cascade, the octenes formed and, where appropriate, higher
oligomers, are separated off from the unconverted butenes and
butanes in the reactor discharge. The oligomers formed may be
purified in a subsequent vacuum fractionation step, giving a pure
octene fraction. During the butene dimerization, small amounts of
dodecenes are generally also obtained. These are preferably
separated off from the octenes prior to the subsequent
reaction.
[0117] In a preferred embodiment, some or all of the reactor
discharge, freed from the oligomers formed and essentially
consisting of unconverted butenes and butanes, is returned. It is
preferable to select the return ratio such that the concentration
of oligomers in the reaction mixture does not exceed 35% by weight,
preferably 20% by weight, based on the hydrocarbon mixture of the
reaction. This measure increases the selectivity of the butene
dimerization in relation to those octenes which, after
hydroformylation, hydrogenation and esterification, give a
particularly preferred alcohol mixture.
[0118] The octenes obtained are converted, in the second process
step, by hydroformylation using synthesis gas in a manner known per
se, into aldehydes having one additional carbon atom. The
hydroformylation of olefins to prepare aldehydes is known per se
and is described, for example, in J. Falbe, (ed.): New Synthesis
with Carbon monoxide, Springer, Berlin, 1980. The hydroformylation
takes place in the presence of catalysts homogeneously dissolved in
the reaction medium. The catalysts generally used here are
compounds or complexes of metals of transition group VIII,
specifically Co, Rh, Ir, Pd, Pt or Ru compounds, or complexes of
these metals, either unmodified or modified, for example, using
amine-containing or phosphine-containing compounds.
[0119] The hydroformylation preferably takes place in the presence
of a cobalt catalyst, in particular dicobaltoctacarbonyl
[CO.sub.2(CO).sub.8]. It preferably takes place at from 120 to
240.degree. C., in particular from 160 to 200.degree. C., and under
a synthesis gas pressure of from 150 to 400 bar, in particular from
250 to 350 bar. The hydroformylation preferably takes place in the
presence of water. The ratio of hydrogen to carbon monoxide in the
synthesis gas mixture used is preferably in the range from 70:30 to
50:50, in particular from 65:35 to 55:45.
[0120] The cobalt-catalyzed hydroformylation process may be carried
out as a multistage process which comprises the following 4 stages:
the preparation of the catalyst (precarbonylation), the catalyst
extraction, the olefin hydroformylation and the removal of the
catalyst from the reaction product (decobaltization). In the first
stage of the process, the precarbonylation, an aqueous cobalt salt
solution, e.g. cobalt formate or cobalt acetate, as starting
material is reacted with carbon monoxide and hydrogen to prepare
the catalyst complex needed for the hydroformylation. In the second
stage of the process, the catalyst extraction, the cobalt catalyst
prepared in the first stage of the process is extracted from the
aqueous phase using an organic phase, preferably using the olefin
to be hydroformylated. Besides the olefin, it is occasionally
advantageous to use the reaction products and byproducts of the
hydroformylation for catalyst extraction, as long as these are
insoluble in water and liquid under the reaction conditions
selected. After the phase separation, the organic phase loaded with
the cobalt catalyst is fed to the third stage of the process, the
hydroformylation. In the fourth stage of the process, the
decobaltization, the organic phase of the reactor discharge is
freed from the cobalt carbonyl complexes in the presence of process
water, which may comprise formic acid or acetic acid, by treatment
with oxygen or air. During this, the cobalt catalyst is destroyed
by oxidation and the resultant cobalt salts are extracted back into
the aqueous phase. The aqueous cobalt salt solution obtained from
the decobaltization is returned to the first stage of the process,
the precarbonylation. The raw hydroformylation product obtained may
be fed directly to the hydrogenation. Another way is to isolate a
C.sub.9 fraction from this in a usual manner, e.g. by distillation,
and feed this to the hydrogenation.
[0121] The formation of the cobalt catalyst, the extraction of the
cobalt catalyst into the organic phase and the hydroformylation of
the olefins can also be carried out in a single-stage process in
the hydroformylation reactor.
[0122] Examples of cobalt compounds which can be used are
cobalt(II) chloride, cobalt(II) nitrate, the amine complexes or
hydrate complexes of these, cobalt carboxylates, such as cobalt
formate, cobalt acetate, cobalt ethylhexanoate and cobalt
naphthenate (Co salts of naphthenic acid), and also the cobalt
caprolactamate complex. Under the conditions of the
hydroformylation, the catalytically active cobalt compounds form in
situ as cobalt carbonyls. It is also possible to use carbonyl
complexes of cobalt such as dicobalt octacarbonyl, tetracobalt
dodecacarbonyl and hexacobalt hexadecacarbonyl.
[0123] The aldehyde mixture obtained during the hydroformylation is
reduced to give primary alcohols. A partial reduction generally
takes place straight away under the conditions of the
hydroformylation, and it is also possible to control the
hydroformylation in such a way as to give essentially complete
reduction. However, the hydroformylation product obtained is
generally hydrogenated in a further process step using hydrogen gas
or a hydrogen-containing gas mixture. The hydrogenation generally
takes place in the presence of a heterogeneous hydrogenation
catalyst. The hydrogenation catalyst used may comprise any desired
catalyst suitable for hydrogenating aldehydes to give primary
alcohols. Examples of suitable commercially available catalysts are
copper chromite, cobalt, cobalt compounds, nickel, nickel
compounds, which, where appropriate, comprise small amounts of
chromium or of other promoters, and mixtures of copper, nickel
and/or chromium. The nickel compounds are generally in a form
supported on support materials, such as alumina or kieselgur. It is
also possible to use catalysts comprising noble metals, such as
platinum or palladium.
[0124] A suitable method of carrying out the hydrogenation is a
trickle-flow method, where the mixture to be hydrogenated and the
hydrogen gas or, respectively, the hydrogen-containing gas mixture
are passed, for example concurrently, over a fixed bed of the
hydrogenation catalyst.
[0125] The hydrogenation preferably takes place at from 50 to
250.degree. C., in particular from 100 to 150.degree. C., and at a
hydrogen pressure of from 50 to 350 bar, in particular from 150 to
300 bar. The desired isononanol fraction in the reaction discharge
obtained during the hydrogenation can be separated off by
fractional distillation from the C.sub.8 hydrocarbons and
higher-boiling products.
[0126] Gas-chromatographic analysis of the resultant alcohol
mixture can give the relative amounts of the individual compounds
(the percentages given being percentages by gas chromatogram
area):
[0127] The proportion of 1-nonanol in the alcohol mixture is
preferably from 6 to 16% by weight, more preferably from 8 to 14%
by weight, related to the overall weight of the alcohol
mixture.
[0128] The proportion of the monomethyloctanols is preferably from
25 to 55% by weight, more preferably from 35 to 55% by weight, and
it is particularly preferable for 6-methyl-1-octanol and
4-methyl-1-octanol together to make up at least 25% by weight, very
particularly preferably at least 35% by weight, related to the
overall weight of the alcohol mixture.
[0129] The proportion of the dimethylheptanols and
monoethylheptanols is preferably from 15 to 60% by weight, more
preferably from 20 to 55% by weight, and it is preferable for
2,5-dimethyl-1-heptanol, 3-ethyl-1-heptanol and
4,5-dimethyl-1-heptanol together to make up at least 15% and in
particular 20% by weight, related to the overall weight of the
alcohol mixture. The proportion of the hexanols is preferably from
4 to 10% by weight and more preferably from 5 to 10% by weight,
related to the overall weight of the alcohol mixture.
[0130] The alcohol mixture is preferably composed of from 70 to
100%, more preferably from 70 to 99%, most preferably from 80 to
98%, and even more preferably from 85 to 95%, of a mixture of
1-nonanol, monomethyloctanols, dimethylheptanols and
monoethylheptanols, related to the overall weight of the alcohol
mixture.
[0131] Preferably the alcohol mixture contains a proportion of 6%
by weight to 16% by weight 1-nonanol, 25% by weight to 55% by
weight monomethyloctanols, 10% by weight to 30% by weight
dimethylheptanols and 7% by weight to 15% by weight
monoethylheptanols, related to the overall weight of the alcohol
mixture.
[0132] Preferably the alcohol mixture is present in a molar ratio
in the range of 1:1 to 2:1, more preferably in a molar ratio in the
range of 1:1 to 1.3:1, in relation to the adipic acid.
[0133] The density of the alcohol mixture of the invention at
20.degree. C. is preferably from 0.75 to 0.9 g/cm.sup.3, more
preferably from 0.8 to 0.88 g/cm.sup.3, and most preferably from
0.82 to 0.84 g/cm.sup.3, according to DIN 51757. The refractive
index n.sub.D.sup.20 is preferably from 1.425 to 1.445, more
preferably from 1.43 to 1.44 and most preferably from 1.432 to
1.438. The boiling range at atmospheric pressure is preferably from
190 to 220.degree. C., more preferably from 195 to 215.degree. C.
and most preferably from 200 to 210.degree. C.
[0134] In a third particularly preferred embodiment, the
dicarboxylic ester component according to the present invention is
a di-(2-ethylhexyl)-adipate (DEHA or DOA).
[0135] The di-(2-ethylhexyl)-adipate preferably has a dynamic
viscosity at 20.degree. C. in the range of 12 to 16 mPas according
to DIN 51562 as calculated from the measured kinematic viscosity
and multiplication of the measured kinematic viscosity with the
density. The di-(2-ethylhexyl)-adipate has a density at 20.degree.
C. in the range of 0.920 to 0.930 g/cm.sup.3 determined according
to DIN 51757 and a pourpoint <-50.degree. C. determined
according to DIN ISO 3016 as lubricant.
[0136] The dynamic viscosity of di-(2-ethylhexyl)-adipate at
20.degree. C. is preferably from 13 to 15 mm.sup.2/s determined
according to DIN 51562.
[0137] Preferably, di-(2-ethylhexyl)-adipate has a density in the
range of 0.922 to 0.928 g/cm.sup.3, more preferably in the range of
0.924 to 0.926 g/cm.sup.3. The density is determined according to
DIN 51757.
[0138] One preferred example for the di-(2-ethylhexyl)-adipate
component is Plastomoll.RTM. DOA which is commercially available
from BASF SE.
[0139] In a fourth particularly preferred embodiment, the
dicarboxylic ester component according to the present invention is
obtainable by reacting a mixture comprising [0140] a) phthalic
acid, optionally in form of its esters or its anhydride, [0141] b1)
a monoalcohol having 10 carbon atoms and a structure of the general
formula I,
[0141] ##STR00008## [0142] wherein [0143] R.sub.1 is selected from
the group consisting of pentyl, iso-pentyl, 2-methyl-butyl,
3-methyl-butyl and 2,2-dimethyl-propyl, [0144] R.sub.2 is H or
methyl, [0145] R.sub.3 is selected from the group consisting of
ethyl, propyl and iso-propyl, [0146] and [0147] b2) a monoalcohol
having 10 carbon atoms and a structure of the general formula
II,
[0147] ##STR00009## [0148] wherein [0149] R.sub.4 is selected from
the group consisting of pentyl, iso-pentyl, 2-methyl-butyl,
3-methyl-butyl and 2,2-dimethyl-propyl, [0150] R.sub.5 is H or
methyl, [0151] R.sub.6 is selected from the group consisting of
ethyl, propyl and iso-propyl, with the proviso that the monoalcohol
b1) and the monoalcohol b2) have a different structure as a
lubricant.
[0152] The viscosity of the polyester at 20.degree. C. is
preferably from 80 to 150 mm.sup.2/s, more preferably from 100 to
140 mm.sup.2/s and most preferably from 115 to 130 mm.sup.2/s
determined according to DIN 51562-1.
[0153] The esters preferably have densities at 20.degree. C.
according to DIN 51757 of from 0.90 to 1.00 g/cm.sup.3, more
preferably from 0.95 to 0.98 g/cm.sup.3 and most preferably from
0.96 to 0.97 g/cm.sup.3. The refractive index n.sub.D.sup.20
according to DIN 51423 is preferably from 1,450 to 1,550, more
preferably from 1,470 to 1,500, and most preferably from 1,480 to
1,485.
[0154] Preferably the ester is a methyl ester or ethyl ester.
[0155] Preferably the monoalcohol b1) is selected from the group
consisting of 2-propylheptanol, 2-propyl-4-methyl-hexanol,
2-propyl-5-methyl-hexanol, 2-isopropyl-4-methyl-hexanol,
2-isopropyl-5-methyl-hexanol, 2-propyl-4,4-dimethylpentanol,
2-ethyl-2,4-dimethylhexanol, 2-ethyl-2-methyl-heptanol,
2-ethyl-2,5-dimethylhexanol and 2-isopropyl-heptanol. More
preferably the monoalcohol b1) is 2-propyl-heptanol.
[0156] Preferably the monoalcohol b2) is selected from the group
consisting of 2-propylheptanol, 2-propyl-4-methyl-hexanol,
2-propyl-5-methyl-hexanol, 2-isopropyl-4-methyl-hexanol,
2-isopropyl-5-methyl-hexanol, 2-propyl-4,4-dimethylpentanol,
2-ethyl-2,4-dimethylhexanol, 2-ethyl-2-methyl-heptanol,
2-ethyl-2,5-dimethylhexanol and 2-isopropyl-heptanol. More
preferably the monoalcohol b2) is 2-propyl-4-methyl-hexanol.
[0157] Preferably the monoalcohols b1) and b2) are present in a
molar ratio in the range of 1.05:1 to 2.0:1, more preferably in the
range of 1.05:1 to 1.5:1, in relation to the phthalic acid a)
[0158] Preferably the weight ratio of monoalcohol b1) to
monoalcohol b2) is in the range of 5:1 to 95:1, more preferably in
the range of 6:1 to 50:1, even more preferably in the range of 10:1
to 40:1, most preferably in the range of 20:1 to 35:1.
[0159] Preferably the mixture further comprises a monoalcohol b3)
having 10 carbon atoms and a structure of the general formula
III,
##STR00010##
wherein [0160] R.sub.7 is selected from the group consisting of
pentyl, iso-pentyl, 2-methyl-butyl, 3-methyl-butyl and
2,2-dimethyl-propyl, [0161] R.sub.8 is H or methyl, [0162] R.sub.9
is selected from the group consisting of ethyl, propyl and
iso-propyl, with the proviso that monoalcohol b3) has a different
structure from both the monoalcohol b1) and the monoalcohol
b2).
[0163] Preferably the monoalcohol b3) is selected from the group
consisting of 2-propylheptanol, 2-propyl-4-methyl-hexanol,
2-propyl-5-methyl-hexanol, 2-isopropyl-4-methyl-hexanol,
2-isopropyl-5-methyl-hexanol, 2-propyl-4,4-dimethylpentanol,
2-ethyl-2,4-dimethylhexanol, 2-ethyl-2-methyl-heptanol,
2-ethyl-2,5-dimethylhexanol and 2-isopropyl-heptanol. More
preferably the monoalcohol b3) is 2-propyl-5-methyl-hexanol.
[0164] Preferably the mixture comprises 80 to 95 weight-% of
2-n-propyl-heptanol as component b1), 1.0 to 10 weight-% of
2-propyl-4-methyl-hexanol as component b2), 1.0 to 10 weight-% of
2-propyl-5-methyl-hexanol as component b3) and 0.1 to 2.0 weight-%
of 2-isopropyl-heptanol, whereby the weight of each component is
related to the total weight of the monoalcohols. More preferably
the mixture comprises 91.0 to 95.0 weight-% of 2-n-propyl-heptanol
as component b1), 2.0 to 5.0 weight-% of 2-propyl-4-methyl-hexanol
as component b2), 3.0 to 5.0 weight-% of 2-propyl-5-methyl-hexanol
as component b3) and 0.1 to 0.8 weight-% of 2-isopropyl-heptanol,
whereby the weight of each component is related to the total weight
of the monoalcohols.
[0165] In another aspect, the presently claimed invention is also
directed to dicarboxylic acid esters which are obtained by reacting
a mixture comprising phthalic acid, optionally in form of its
esters or its anhydride, 2-propyl-heptanol,
2-propyl-4-methyl-hexanol and 2-propyl-5-methyl-hexanol. The most
preferred dicarboxylic acid ester according to the fourth
particularly preferred embodiment is di-(propylheptyl)-phthalate
(DPHP). This compound is also commercially available as
Palatinol.RTM. (BASF SE).
[0166] In another aspect, the dicarboxylic acid esters are obtained
by reacting a mixture comprising phthalic acid, optionally in form
of its esters or its anhydride, and 80 to 95 weight-% of
2-n-propyl-heptanol, 1.0 to 10 weight. % of
2-propyl-4-methyl-hexanol, 1.0 to 10 weight-% of
2-propyl-5-methyl-hexanol and 0.1 to 2.0 weight-% of
2-isopropyl-heptanol, whereby the weight of each component is
related to the total weight of the monoalcohols.
[0167] In another particularly preferred embodiment of the present
invention, the lubricant composition according to the present
invention includes at least one of the four above particularly
preferred dicarboxylic acid esters while further comprising an
additional monocarboxylic acid ester component.
[0168] The additional monocarboxylic acid ester component is
preferably obtained by reacting one or more monoalcohols with a
monocarboxylic acid.
[0169] The monocarboxylic acids preferably contain at least 4
carbons, preferably C.sub.6 to C.sub.30, more preferably C.sub.8 to
C.sub.20, acids such as saturated straight chain fatty acids
including caprylic acid, capric acid, lauric acid, myristic acid,
palmitic acid, stearic acid, arachic acid, and behenic acid, or the
corresponding branched chain fatty acids or unsaturated fatty acids
such as oleic acid, or mixtures thereof.
[0170] The monoalcohol preferably is 2-ethylhexanol,
propylheptanol, or the like.
[0171] Other typical monocarboxylic acid ester components are
represented by 2-ethylhexyl oleate, e.g. commercially available as
Synative ES EHO.RTM. (BASF SE), 2-ethylhexyl cocoate, e.g.
commercially available as Synative ES EHK.RTM. (BASF SE),
2-ethylhexyl palmitate, e.g. commercially available as Synative ES
EHPA.RTM. (BASF SE), 2-ethylhexylstearate, e.g. commercially
available as Synative ES EHS.RTM. (BASF SE), 2-ethylhexyl
tallowate, e.g. commercially available as Synative ES EHTI.RTM.
(BASF SE).
[0172] The amount of additional monocarboxylic acid ester in the
lubricant compositions according to the present invention is in the
range of from 0 to 25 wt %, preferably in the range of from 5 to 20
wt %, or even more preferably in the range of from 10 to 18 wt %
based on the total weight of the lubricant composition.
[0173] In another particularly preferred embodiment of the present
invention, the lubricant composition according to the present
invention includes at least one of the four above particularly
preferred dicarboxylic acid esters, optionally an additional
monocarboxylic acid ester, while further comprising an additional
complex carboxylic acid ester component.
[0174] A complex carboxylic acid ester according to the present
invention is defined as an ester which is formed from polyols with
dicarboxylic acids and/or monocarboxylic acids.
[0175] The complex monocarboxylic acid ester component is
preferably obtained by reacting one or more polyhydric alcohols,
preferably the hindered polyols such as the neopentyl polyols, e.g.
neopentyl glycol, trimethylol ethane,
2-methyl-2-propyl-1,3-propanediol, trimethylol propane, trimethylol
butane, pentaerythritol and dipentaerythritol with monocarboxylic
acids containing at least 4 carbons, normally the C.sub.5 to
C.sub.30 acids such as saturated straight chain fatty acids
including caprylic acid, capric acid, lauric acid, myristic acid,
palmitic acid, stearic acid, arachic acid, and behenic acid, or the
corresponding branched chain fatty acids or unsaturated fatty acids
such as oleic acid, or mixtures thereof, with polycarboxylic
acids.
[0176] For example, a neopentyl glycol ester of at least one
monocarboxylic acid having from 7 to 10 carbon atoms and of at
least one other ester of a different hindered polyol with a
monocarboxylic acid having from 5 to 10 carbon atoms is preferred.
Other preferred polyols are trimethylolpropane, pentaerythritol, or
dipentaerythritol.
[0177] Another typical complex carboxylic acid ester that is
preferably used in the lubricant compositions according to the
present invention is a complex carboxylic acid ester commercially
available as Synative ES 3345.RTM. (BASF SE).
[0178] The amount of additional complex carboxylic acid ester in
the lubricant compositions according to the present invention is in
the range of from 0 to 20 wt %, preferably in the range of from 2
to 15 wt %, or even more preferably in the range of from 5 to 10 wt
% based on the total weight of the lubricant composition.
[0179] In another particularly preferred embodiment of the present
invention, the lubricant composition according to the present
invention comprises at least one of the four above particularly
preferred dicarboxylic acid esters, optionally an additional
monocarboxylic acid ester and/or an additional complex carboxylic
acid ester component, further comprising an additional Guerbet
alcohol component.
[0180] The term Guerbet alcohols is used for 2-alkyl-substituted
1-alkanols whose industrial synthesis is described inter alia in H.
Machemer, Angewandte Chemie, Vol. 64, pages 213-220 (1952) and in
G. Dieckelmann and H. J. Heinz in "The Basics of Industrial
Oleochemistry", pages 145-145 (1988). In one preferred embodiment
the Guerbet alcohol is derived at least partly from 2-hexyl
decanol, 2-hexyl dodecanol, 2-octyl decanol and/or 2-octyl
dodecanol.
[0181] Particularly preferred Guerbet alcohols are 2-hexyldecyl
alcohol, e.g. commercially available as Synative AL G 16.RTM. (BASF
SE), or 2-octyldodecyl alcohol, e.g. commercially available as
Synative AL G 20.RTM. (BASF SE).
[0182] The amount of additional Guerbet alcohol component in the
lubricant compositions according to the present invention is in the
range of from 0 to 20 wt %, preferably in the range of from 2 to 15
wt %, or even more preferably in the range of from 5 to 10 wt %
based on the total weight of the lubricant composition.
[0183] The base oil (or base stock) to be used in the lubricant
compositions according to the present invention is an optional
component.
[0184] The base oil to be used in the lubricant compositions
according to the present invention is an inert, solvent-type oil
component in the lubricant compositions according to the present
invention.
[0185] Preferably, the lubricant compositions according to the
present invention further comprise base oils 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
and phosphate esters (Group V oils).
[0186] Definitions for the base oils according to the present
invention 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
stocks as follows:
[0187] a) Group I base oils contain less than 90 percent saturates
and/or greater than 0.03 percent sulfur and have a viscosity index
greater than or equal to 80 and less than 120 using the test
methods specified in the following table.
[0188] 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 using the test methods specified in the following table.
[0189] 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 using the test
methods specified in the following table
[0190] Analytical Methods for Base Stock:
TABLE-US-00004 Property Test Method Saturates ASTM D 2007 Viscosity
index ASTM D 2270 Sulfur ASTM D 2622 ASTM D 4294 ASTM D 4927 ASTM D
3120
[0191] d) Group IV base oils contain polyalphaolefins. Synthetic
lower viscosity fluids suitable for the present invention include
the polyalphaolefins (PAOs) and the synthetic oils from the
hydrocracking or hydro-isomerization of Fischer Tropsch high
boiling fractions including waxes. These are both base oils
comprised of saturates with low impurity levels consistent with
their synthetic origin. The hydro-isomerized Fischer Tropsch waxes
are highly suitable base oils, comprising saturated components of
iso-paraffinic character (resulting from the isomerization of the
predominantly n-paraffins of the Fischer Tropsch waxes) which give
a good blend of high viscosity index and low pour point. Processes
for the hydro-isomerization of Fischer Tropsch waxes are described
in U.S. Pat. Nos. 5,362,378; 5,565,086; 5,246,566 and 5,135,638, as
well in EP 710710, EP 321302 and EP 321304.
[0192] Polyalphaolefins suitable for the lubricant compositions
according to the present invention, include known PAO materials
which typically comprise relatively low molecular weight
hydrogenated polymers or oligomers of alphaolefins which include
but are not limited to C.sub.2 to about C.sub.32 alphaolefins with
the C.sub.8 to about C.sub.16 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, although the dimers of higher olefins in the range
of C.sub.14 to C.sub.18 provide low viscosity base stocks.
[0193] Terms like PAO-2, PAO 4, PAO 6 or PAO 8 represent preferred
polyalphaolefins while these terms are commonly used specifications
for different classes of polyalphaolefins characterized by their
respective viscosity. For instance, PAO 2 refers to a particularly
preferred class of polyalphaolefins according to the present
invention which typically has a viscosity in the range of 2
mm.sup.2/s at 100.degree. C. A variety of commercially available
compositions are available for these specifications.
[0194] Low viscosity PAO fluids suitable for the lubricant
compositions according to the present invention, may be
conveniently made by the polymerization of an alphaolefin in the
presence of a polymerization catalyst such as the Friedel-Crafts
catalysts including, for example, aluminum trichloride, boron
trifluoride or complexes of boron trifluoride with water, alcohols
such as ethanol, propanol or butanol, carboxylic acids or esters
such as ethyl acetate or ethyl propionate. For example, the methods
disclosed by U.S. Pat. Nos. 3,149,178 or 3,382,291 may be
conveniently used herein. Other descriptions of PAO synthesis are
found in the following U.S. Pat. No. 3,742,082 (Brennan); U.S. Pat.
No. 3,769,363 (Brennan); U.S. Pat. No. 3,876,720 (Heilman); U.S.
Pat. No. 4,239,930 (Allphin); U.S. Pat. No. 4,367,352 (Watts); U.S.
Pat. No. 4,413,156 (Watts); U.S. Pat. No. 4,434,308 (Larkin); U.S.
Pat. No. 4,910,355 (Shubkin); U.S. Pat. No. 4,956,122 (Watts); and
U.S. Pat. No. 5,068,487 (Theriot).
[0195] e) Group V base oils contain any base stocks not described
by Groups I to IV. Examples of Group V base oils include alkyl
naphthalenes, alkylene oxide polymers, silicone oils and phosphate
esters.
[0196] Carboxylic acid esters which are widely considered in the
literature to belong to the Group V base oils are not understood
according to the present invention as base oils (base stocks) or
even group V base oils but are separately classified or defined as
the dicarboxylic acid ester or monocarboxylic acid ester component
being either essential or at least optional to the present
invention, respectively.
[0197] 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.
[0198] 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-polyiso-propylene 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 polycarboxylic
esters thereof, for example, the acetic acid esters, mixed
C.sub.3-C.sub.8 fatty acid esters and C.sub.13 Oxo acid diester of
tetraethylene glycol.
[0199] Silicon-based oils such as the polyalkyl-, polyaryl-,
polyalkoxy- or polyaryloxysilicone oils and silicate 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, oly(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.
[0200] The base oil may also include so-called gas-to-liquid (GTL)
base stocks. Suitable GTL base stocks that can be used in the
present invention are for instance described in WO 2010/021751 A1
and are herewith incorporated by reference.
[0201] The base oil component has a kinematic viscosity according
to DIN 51562-1 at 100.degree. C. in the range of from 1 to 8
mm.sup.2/s, preferably of from 1 to 5 mm.sup.2/s, or even more
preferably of from 1 to 3 mm.sup.2/s. PAO-2 is the most preferred
base oil to be used in the lubricant compositions according to the
present invention.
[0202] The relative amount of base oil in the lubricant
compositions according to the present invention is in the range of
0 to 50 wt %, preferably in the range of from 5 to 35, or even more
preferably in the range of 10 to 25 wt % based on the total amount
of lubricant composition.
[0203] Oligomeric copolymers are preferably ethylene-propylene
copolymers having a number average molecular weight Mn according to
industrial standard DIN 55672 within the range of about 20000 to
about 150000 kg/mol, preferably of from about 40000 to about 120000
kg/mol, or even more preferably of from 60000 to 100000 kg/mol.
Such oligomeric copolymers are for instance described in U.S. Pat.
No. 5,451,630. Oligomeric copolymers are typically used in the art
as viscosity modifying agents in lubricant compositions with
improved shear stability.
[0204] The ethylene propylene copolymers according to the present
invention have a kinematic viscosity according to JIS K 2283 at
100.degree. C. in the range of from 500 to 3000 mm.sup.2/s,
preferably of from 900 to 2500 mm.sup.2/s, or even more preferably
of from 1000 to 2200 mm.sup.2/s.
[0205] The ethylene propylene copolymers according to the present
invention have a kinematic viscosity according to JIS K 2283 at
40.degree. C. in the range of from 10000 to 50000 mm.sup.2/s,
preferably of from 15000 to 40000 mm.sup.2/s, or even more
preferably of from 18000 to 38000 mm.sup.2/s.
[0206] The ethylene propylene copolymers according to the present
invention have a pourpoint according to JIS K 2269 in the range of
from -20.degree. C. to -5.degree. C., preferably of from
-15.degree. C. to -10.degree. C., or even more preferably of from
-12.5 to -10.degree. C.
[0207] Another preferred type of ethylene propylene copolymers is
commercially available as LUCANT.TM. (Mitsui Chemicals), preferably
LUCANT.TM.2000 and LUCANT.TM.1100.
[0208] The amount of oligomeric copolymer, preferably ethylene
propylene copolymer, is in the range of about 5 to 30 wt %.
preferably 10 to 25 wt %, or even more preferably 12 to 20 wt %
based on the total weight of the lubricant composition.
[0209] The ratio of the dicarboxylic acid ester component to the
oligomeric copolymers in the lubricant compositions according to
the present invention is in the range of from 2:1 to 19:1,
preferably 3:1 to 10:1, even more preferably in the range of from
4:1 to 6:1 based on the relative weight of these components in the
lubricant compositions according to the present invention.
[0210] The lubricant composition according to the present invention
comprising oligomeric copolymers as viscosity index improving
agents can further comprise additional viscosity index improving
agents. Viscosity index improving agents are thickener components
that are able to increase the viscosity of a lubricant composition
when added to it.
[0211] Additional suitable viscosity index improving agents
typically include conventional polyisobutenes (PIBs) having no
terminal double bonds, highly reactive polyisobutenes having
terminal double bonds, polymethacrylates (PMAs) or the like.
[0212] However, in a preferred embodiment of the present invention,
the just mentioned, additional viscosity index improving agents
apart from oligomeric copolymers are absent from the lubricant
compositions according to the present invention, either
individually or in combination.
[0213] Accordingly, in a preferred embodiment of the present
invention, conventional polyisobutenes (PlBs) without terminal
double bonds and/or highly reactive polyisobutenes are absent from
the lubricant compositions according to the present invention.
[0214] The term "conventional polyisobutenes" as used in the
present application relates to polyisobutenes which do not have
terminal double bonds. Conventional polyisobutenes therefore differ
in the latter aspect from the highly reactive polyisobutenes which
have high degree of terminal double bonds. One preferred
conventional polyisobutene is Lubrizol 8406.RTM..
[0215] Highly reactive polyisobutene polymers are understood in
their most generic manner in the context of the present invention
as a polyisobutene polymer having at least 60 mol % terminal double
bonds based on the total number of double bonds in the polymer. The
amount of terminal double bonds in the highly reactive
polyisobutenes can be determined following the method mentioned in
U.S. Pat. No. 5,962,604 using .sup.13C-NMR spectroscopy based on
the relative peak areas corresponding to the signals for the
C-alpha and C-beta carbon atom (chemical shift of 114.4 ppm and
143.6 ppm), respectively.
[0216] In another preferred embodiment of the present invention,
poly(meth)acrylates (PMAs) are absent from the lubricant
compositions according to the present invention.
[0217] Poly(meth)acrylates (PMAs) are esters of (meth)acrylic acid
that are able to provide improved shear stability in lubricant
compositions. Such poly(meth)acrylates are for instance described
in DE 3544061. Typical PMAs used in the art are those from the
commercial Viscoplex.RTM. series of additives. Preferred PMAs are
alkylmethacrylate (Viscoplex 0-101), alkylmaleate-alpha-olefin
copolymer I (Gear-Lube 7930), alkylfumarate-alpha-olefin-copolymer
I (Gear-Lube 7960) and the like.
[0218] The lubricant compositions according to the present
invention may also comprise an additive component.
[0219] The additive component as used in the present invention may
include an additive package and/or performance additives.
[0220] The additive package as used in the present invention as
well as the compounds relating to performance additives are
considered mixtures of additives that are typically used in
lubricant compositions in limited amounts for mechanically,
physically or chemically stabilizing the lubricant compositions
while special performance characteristics can be further
established by the individual or combined presence of such selected
additives.
[0221] Additive packages are separately defined in the present
invention since a variety of such additive packages are
commercially available and typically used in lubricant
compositions. One such preferred additive package that is
commercially available is marketed under the name
Anglamol6004J.RTM..
[0222] However, the individual components contained in the additive
packages and/or the compounds further defined in the present
invention as so-called performance additives include a larger
number of different types of additives including dispersants, metal
deactivators, detergents, extreme pressure agents (typically boron-
and/or sulfur- and/or phosphorus-containing), antiwear agents,
antioxidants (such as hindered phenols, aminic antioxidants or
molybdenum compounds), corrosion inhibitors, foam inhibitors,
demulsifiers, pour point depressants, seal swelling agents,
friction modifiers and mixtures thereof.
[0223] The additive component as the sum of all additives contained
in the lubricant compositions according to the present invention
also including all additives contained in an additive package or
added separately is present in the lubricant compositions of the
present invention in an amount of 0 to 20 wt %, preferably 0.1 to
15 wt %, more preferably 2 to 12 wt %, and most preferably in an
amount of 3 to 10 wt %.
[0224] Extreme pressure agents include compounds containing boron
and/or sulfur and/or phosphorus. The extreme pressure agent may be
present in the lubricant compositions at 0% by weight to 20% by
weight, or 0.05% by weight to 10% by weight, or 0.1% by weight to
8% by weight of the lubricant composition.
[0225] In one embodiment according to the present invention, the
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.
[0226] In one embodiment the sulfurised olefin includes a
sulfurised olefin derived from propylene, isobutylene, pentene or
mixtures thereof.
[0227] In one embodiment according to the present invention, the
extreme pressure agent 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.
[0228] In one embodiment, the dimercaptothiadiazole may be a
thiadiazole-functionalised dispersant. A detailed description of
the thiadiazole-functionalised dispersant is described is
paragraphs [0028] to [0052] of International Publication WO
2008/014315.
[0229] The thiadiazole-functionalised dispersant may be prepared by
a method including heating, reacting or complexing a thiadiazole
compound with a dispersant substrate. The thiadiazole compound may
be covalently bonded, salted, complexed or otherwise solubilised
with a dispersant, or mixtures thereof.
[0230] The relative amounts of the dispersant substrate and the
thiadiazole used to prepare the thiadiazole-functionalised
dispersant may vary. In one embodiment the thiadiazole compound is
present at 0.1 to 10 parts by weight relative to 100 parts by
weight of the dispersant substrate. In different embodiments the
thiadiazole compound is present at greater than 0.1 to 9, or
greater than 0.1 to less than 5, or 0.2 to less than 5: to 100
parts by weight of the dispersant substrate. The relative amounts
of the thiadiazole compound to the dispersant substrate may also be
expressed as (0.1-10):100, or (>0.1-9):100, (such as
(>0.5-9):100), or (0.1 to less than 5): 100, or (0.2 to less
than 5): 100.
[0231] In one embodiment the dispersant substrate is present at 0.1
to 10 parts by weight relative to 1 part by weight of the
thiadiazole compound. In different embodiments the dispersant
substrate is present at greater than 0.1 to 9, or greater than 0.1
to less than 5, or about 0.2 to less than 5: to 1 part by weight of
the thiadiazole compound. The relative amounts of the dispersant
substrate to the thiadiazole compound may also be expressed as
(0.1-10):1, or (>0.1-9):1, (such as (>0.5-9):1), or (0.1 to
less than 5): 1, or (0.2 to less than 5): 1.
[0232] The thiadiazole-functionalised dispersant may be derived
from a substrate that includes a succinimide dispersant (for
example, N-substituted long chain alkenyl succinimides, typically a
polyisobutylene succinimide), 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, a polyetheramine dispersant, a
viscosity modifier containing dispersant functionality (for example
polymeric viscosity index modifiers containing dispersant
functionality), or mixtures thereof. In one embodiment the
dispersant substrate includes a succinimide dispersant, an
ester-containing dispersant or a Mannich dispersant.
[0233] In one embodiment according to the present invention, the
extreme pressure agent includes a boron-containing compound. The
boron-containing compound includes a borate ester (which in some
embodiments may also be referred to as a borated epoxide), a
borated alcohol, a borated dispersant, a borated phospholipid or
mixtures thereof. In one embodiment the boron-containing compound
may be a borate ester or a borated alcohol.
[0234] The borate ester may be prepared by the reaction of a boron
compound and at least one compound selected from epoxy compounds,
halohydrin compounds, epihalohydrin compounds, alcohols and
mixtures thereof. The alcohols include dihydric alcohols, trihydric
alcohols or higher alcohols, with the proviso for one embodiment
that hydroxyl groups are on adjacent carbon atoms, i.e.,
vicinal.
[0235] Boron compounds suitable for preparing the borate ester
include the various forms selected from the group consisting of
boric acid (including metaboric acid, orthoboric acid and
tetraboric acid), boric oxide, boron trioxide and alkyl borates.
The borate ester may also be prepared from boron halides.
[0236] In one embodiment suitable borate ester compounds include
tripropyl borate, tributyl borate, tripentyl borate, trihexyl
borate, triheptyl borate, trioctyl borate, trinonyl borate and
tridecyl borate. In one embodiment the borate ester compounds
include tributyl borate, tri-2-ethylhexyl borate or mixtures
thereof.
[0237] In one embodiment, the boron-containing compound is a
borated dispersant, typically derived from an N-substituted long
chain alkenyl succinimide. In one embodiment the borated dispersant
includes a polyisobutylene succinimide. Borated dispersants are
described in more detail in U.S. Pat. Nos. 3,087,936; and
3,254,025.
[0238] In one embodiment the borated dispersant may be used in
combination with a sulfur-containing compound or a borate
ester.
[0239] In one embodiment the extreme pressure agent is other than a
borated dispersant.
[0240] The number average molecular weight Mn (GPC; kg/mol) of the
hydrocarbon from which the long chain alkenyl group was derived
includes ranges of 350 to 5000, or 500 to 3000, or 550 to 1500. The
long chain alkenyl group may have a number average molecular weight
Mn of 550, or 750, or 950 to 1000.
[0241] The N-substituted long chain alkenyl succinimides are
borated using a variety of agents including boric acid (for
example, metaboric acid, orthoboric acid and tetraboric acid),
boric oxide, boron trioxide, and alkyl borates. In one embodiment
the borating agent is boric acid which may be used alone or in
combination with other borating agents.
[0242] The borated dispersant may be prepared by blending the boron
compound and the N-substituted long chain alkenyl succinimides and
heating them at a suitable temperature, such as, 80.degree. C. to
250.degree. C., or 90.degree. C. to 230.degree. C., or 100.degree.
C. to 210.degree. C., until the desired reaction has occurred. The
molar ratio of the boron compounds to the N-substituted long chain
alkenyl succinimides may have ranges including 10:1 to 1:4, or 4:1
to 1:3; or the molar ratio of the boron compounds to the
N-substituted long chain alkenyl succinimides may be 1:2.
Alternatively, the ratio of moles B:moles N (that is, atoms of
B:atoms of N) in the borated dispersant may be 0.25:1 to 10:1 or
0.33:1 to 4:1 or 0.2:1 to 1.5:1, or 0.25:1 to 1.3:1 or 0.8:1 to
1.2:1 or about 0.5:1 An inert liquid may be used in performing the
reaction. The liquid may include toluene, xylene, chlorobenzene,
dimethylformamide or mixtures thereof.
[0243] In one embodiment, the additive component in the lubricant
composition according to the present invention further includes a
borated phospholipid. The borated phospholipid may be derived from
boronation of a phospholipid (for example boronation may be carried
out with boric acid). Phospholipids and lecithins are described in
detail in Encyclopedia of Chemical Technology, Kirk and Othmer, 3rd
Edition, in "Fats and Fatty Oils", Volume 9, pages 795-831 and in
"Lecithins", Volume 14, pages 250-269.
[0244] The phospholipid may be any lipid containing a phosphoric
acid, such as lecithin or cephalin, or derivatives thereof.
Examples of phospholipids include phosphatidylcholine,
phosphatidylserine, phosphatidylinositol,
phosphatidyl-ethanolamine, phosphotidic acid and mixtures thereof.
The phospholipids may be glycerophospholipids, glycerol derivatives
of the above list of phospholipids. Typically, the
glycerophospholipids have one or two acyl, alkyl or alkenyl groups
on a glycerol residue. The alkyl or alkenyl groups may contain 8 to
30, or 8 to 25, or 12 to 24 carbon atoms. Examples of suitable
alkyl or alkenyl groups include octyl, dodecyl, hexadecyl,
octadecyl, docosanyl, octenyl, dodecenyl, hexadecenyl and
octadecenyl.
[0245] Phospholipids may be prepared synthetically or derived from
natural sources. Synthetic phospholipids may be prepared by methods
known to those in the art. Naturally derived phospholipids are
often extracted by procedures known to those in the art.
Phospholipids may be derived from animal or vegetable sources. A
useful phospholipid is derived from sunflower seeds. The
phospholipid typically contains 35% to 60% phosphatidylcholine, 20%
to 35% phosphatidylinositol, 1% to 25% phosphatidic acid, and 10%
to 25% phosphatidylethanolamine, wherein the percentages are by
weight based on the total phospholipids. The fatty acid content may
be 20% by weight to 30% by weight palmitic acid, 2% by weight to
10% by weight stearic acid, 15% by weight to 25% by weight oleic
acid, and 40% by weight to 55% by weight linoleic acid.
[0246] In another embodiment, the performance additive in the
lubricant compositions according to the present invention may
include a friction modifier. A friction modifier is any material or
materials that can alter the coefficient of friction of a surface
lubricated by any lubricant or fluid containing such material(s).
Friction modifiers, also known as friction reducers, or lubricity
agents or oiliness agents, and other such agents that change the
ability of base oils, formulated lubricant compositions, or
functional fluids, to modify the coefficient of friction of a
lubricated surface may be effectively used in combination with the
base oils or lubricant compositions of the present invention if
desired. Friction modifiers may include metal-containing compounds
or materials as well as ashless compounds or materials, or mixtures
thereof. Metal-containing friction modifiers may 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.
[0247] 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.
[0248] In one embodiment, the performance additive in the lubricant
compositions according to the present invention may include
phosphorus- or sulfur-containing anti-wear agents other than
compounds described as an extreme pressure agent of the amine salt
of a phosphoric acid ester described above. Examples of the
anti-wear agent may include a non-ionic phosphorus compound
(typically compounds having phosphorus atoms with an oxidation
state of +3 or +5), a metal dialkyldithiophosphate (typically zinc
dialkyldithiophosphates), amine dithiophosphate, ashless
dithiophosphates and a metal mono- or di-alkylphosphate (typically
zinc phosphates), or mixtures thereof.
[0249] The non-ionic phosphorus compound includes a phosphite
ester, a phosphate ester, or mixtures thereof.
[0250] In one embodiment, the performance additive in the lubricant
composition according to the present invention may further include
at least one antioxidant. Antioxidants retard the oxidative
degradation of base stocks during service. Such degradation may
result in deposits on metal surfaces, the presence of sludge, or a
viscosity increase in the lubricant. One skilled in the art knows a
wide variety of oxidation inhibitors that are useful in lubricating
oil compositions.
[0251] Useful antioxidants include hindered phenols. These phenolic
antioxidants may be ashless (metal-free) phenolic compounds or
neutral or basic metal salts of certain phenolic compounds. Typical
phenolic antioxidant compounds are the hindered phenolics which are
the ones which contain a sterically hindered hydroxyl group, and
these include those derivatives of dihydroxy aryl compounds in
which the hydroxyl groups are in the o- or p-position to each
other. Typical phenolic antioxidants include the hindered phenols
substituted with C.sub.6+ alkyl groups and the alkylene coupled
derivatives of these hindered phenols. Examples of phenolic
materials of this type 2-t-butyl-4-heptyl phenol; 2-t-butyl-4-octyl
phenol; 2-t-butyl-4-dodecyl phenol; 2,6-di-t-butyl-4-heptyl phenol;
2,6-di-t-butyl-4-dodecyl phenol; 2-methyl-6-t-butyl-4-heptyl
phenol; and 2-methyl-6-t-butyl-4-dodecyl phenol. Other useful
hindered mono-phenolic antioxidants may include for example
hindered 2,6-di-alkyl-phenolic propionic ester derivatives.
Bis-phenolic antioxidants may also be advantageously used in
combination with the instant invention. Examples of ortho-coupled
phenols include: 2,2'-bis(4-heptyl-6-t-butyl-phenol); 2,2'-bis(4-
octyl-6-t-butyl-phenol); and 2,2'-bis(4-dodecyl-6-t-butyl-phenol).
Para-coupled bisphenols include for example 4,4'-bis(2,6-di-t-butyl
phenol) and 4,4'- methylene-bis(2,6-di-t-butyl phenol).
[0252] Non-phenolic oxidation inhibitors which may be used include
aromatic amine antioxidants and these may be used either as such or
in combination with phenolics. Typical examples of non-phenolic
antioxidants include: alkylated and non-alkylated aromatic amines
such as aromatic monoamines of the formula R.sup.8R.sup.9R.sup.10N,
where R.sup.8 is an aliphatic, aromatic or substituted aromatic
group, R.sup.9 is an aromatic or a substituted aromatic group, and
R.sup.10 is H, alkyl, aryl or R.sup.11S(O).sub.xR.sup.12, where
R.sup.11 is an alkylene, alkenylene, or aralkylene group, R.sup.12
is a higher alkyl group, or an alkenyl, aryl, or alkaryl group, and
x is 0, 1 or 2. The aliphatic group R.sup.8 may contain from 1 to
about 20 carbon atoms, and preferably contains from about 6 to 12
carbon atoms. The aliphatic group is a saturated aliphatic group.
Preferably, both R.sup.8 and R.sup.9 are aromatic or substituted
aromatic groups, and the aromatic group may be a fused ring
aromatic group such as naphthyl. Aromatic groups R.sup.8 and
R.sup.9 may be joined together with other groups such as S.
[0253] Typical aromatic amines antioxidants have alkyl substituent
groups of at least about 6 carbon atoms. Examples of aliphatic
groups include hexyl, heptyl, octyl, nonyl, and decyl. Generally,
the aliphatic groups will not contain more than about 14 carbon
atoms. The general types of amine antioxidants useful in the
present compositions include diphenylamines, phenyl naphthylamines,
phenothiazines, imidodibenzyls and diphenyl phenylene diamines.
Mixtures of two or more aromatic amines are also useful. Polymeric
amine antioxidants can also be used. Particular examples of
aromatic amine antioxidants useful in the present invention
include: p,p'-dioctyldiphenylamine;
t-octylphenyl-alpha-naphthylamine; phenyl-alphanaphthylamine; and
p-octylphenyl-alpha-naphthylamine. Sulfurized alkyl phenols and
alkali or alkaline earth metal salts thereof also are useful
antioxidants.
[0254] In one embodiment, the performance additive in the lubricant
compositions according to the present invention further includes a
dispersant. 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 hydrocarbylamine
dispersant, a polyether dispersant or a polyetheramine
dispersant.
[0255] 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 400 to 5000, or 950 to 1600.
Succinimide dispersants and their methods of preparation are more
fully described in U.S. Pat. Nos. 4,234,435 and 3,172,892. Suitable
ester-containing dispersants are typically high molecular weight
esters. These materials are described in more detail in U.S. Pat.
No. 3,381,022.
[0256] 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 400 to 5000. Borated dispersants
are described in more detail above within the extreme pressure
agent description.
[0257] Dispersant viscosity modifiers (often referred to as DVMs)
are considered additives in the context of the present invention
due to their additional functionalisation and are therefore not
considered viscosity improving agents according to the present
invention. Dispersant viscosity modifiers include functionalised
polyolefins, for example, ethylene-propylene copolymers that have
been functionalised with the reaction product of maleic anhydride
and an amine, a polymethacrylate functionalised with an amine, or
esterified styrene-maleic anhydride copolymers reacted with an
amine.
[0258] As another type of performance additives, corrosion
inhibitors can be described as any materials (additives,
functionalised fluids, etc.) that form a protective film on a
surface that prevents corrosion agents from reacting or attacking
that surface with a resulting loss of surface material. Protective
films may be absorbed on the surface or chemically bonded to the
surface. Protective films may be constituted from mono-molecular
species, oligomeric species, polymeric species, or mixtures
thereof. Protective films may derive from the intact corrosion
inhibitors, from their combination products, or their degradation
products, or mixtures thereof. Surfaces that may benefit from the
action of corrosion inhibitors may include metals and their alloys
(both ferrous and non-ferrous types) and non-metals.
[0259] 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
alkylaryl-versions 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.
[0260] Corrosion inhibitors are used to reduce the degradation of
metallic parts that are in contact with the lubricant composition.
Suitable corrosion inhibitors include thiadiazoles. Aromatic
triazoles, such as tolyltriazole, are suitable corrosion inhibitors
for non-ferrous metals, such as copper.
[0261] Metal deactivators include derivatives of benzotriazoles
(typically tolyltriazole), 1,2,4-triazoles, benzimidazoles,
2-alkyldithiobenzimidazoles, thiadiazoles or
2-alkyldithiobenzothiazoles.
[0262] Foam inhibitors may also advantageously be added as a
performance additive to the lubricant compositions according to the
present invention. These agents retard the formation of stable
foams. Silicones and organic polymers are typical foam inhibitors.
For example, polysiloxanes, such as silicon oil, or
polydimethylsiloxane, provide foam inhibiting properties. Further
foam inhibitors include copolymers of ethyl acrylate and
2-ethylhexyl acrylate and optionally vinyl acetate.
[0263] Demulsifiers include trialkyl phosphates, and various
polymers and copolymers of ethylene glycol, ethylene oxide,
propylene oxide, or mixtures thereof.
[0264] As pour point depressants, esters of maleic
anhydride-styrene, or polyacrylamides are included.
[0265] As a further performance additive to be used in the
lubricant compositions according to the present invention, seal
compatibility agents help to swell elastomeric seals by causing a
chemical reaction in the fluid or physical change in the elastomer.
Suitable seal compatibility agents for lubricant compositions
include organic phosphates, aromatic esters, aromatic hydrocarbons,
esters (butylbenzyl phthalate, for example), and polybutenyl
succinic anhydride. Such additives may preferably be used in an
amount of 0.01 to 3% by weight, more preferably 0.01 to 2% by
weight of the total amount of the lubricant composition.
[0266] The present invention provides lubricant compositions which
have excellent low temperature viscosity and very good rheological
properties including shear stability over a broad temperature
range. Particularly, the lubricant compositions according to the
present invention have high permanent shear stability. The
lubricant compositions according to the present invention also have
very good oxidation stability.
[0267] One preferred lubricant composition according to the present
invention as further illustrated by inventive example 1 (IE-1) is
as follows:
TABLE-US-00005 Lubricant composition Dicarboxylic acid ester
component having kinematic 70 to 95 wt % viscosity according to DIN
51562-1 at 100.degree. C. in the range of from 2 to 5 mm.sup.2/s
Ethylene-propylene copolymer having kinematic 5 to 30 wt %
viscosity according to JIS K 2283 at 100.degree. C. in the range of
from 1900 to 2100 mm.sup.2/s
[0268] Another preferred lubricant composition according to the
present invention is defined as follows:
TABLE-US-00006 Lubricant composition Di-(2-propylheptyl)adipate
(DPHA) 70 to 95 wt % Ethylene-propylene copolymer having kinematic
5 to 30 wt % viscosity according to JIS K 2283 at 100.degree. C. in
the range of from 1900 to 2100 mm.sup.2/s
[0269] Another preferred lubricant composition according to the
present invention as further illustrated by inventive example 2
(IE-2) is defined as follows:
TABLE-US-00007 Lubricant composition Dicarboxylic acid ester
component having dynamic 60-80 wt % viscosity according to DIN
51562-1 at 100.degree. C. in the range of from 12 to 16 mm.sup.2/s
Ethylene-propylene copolymer having kinematic 10 to 25 wt %
viscosity according to JIS K 2283 at 100.degree. C. in the range of
from 1000 to 1200 mm.sup.2/s Monocarboxylic acid ester having
kinematic viscosity 10 to 25 wt % according to DIN 51562-1 at
100.degree. C. in the range of from 2 to 4 mm.sup.2/s
[0270] Another preferred lubricant composition according to the
present invention as further illustrated by inventive examples 3
(IE-3) and 4 (IE-4) is defined as follows:
TABLE-US-00008 Lubricant composition Dicarboxylic acid ester
component having dynamic 55-75 wt % viscosity according to DIN
51562-1 at 100.degree. C. in the range of from 12 to 16 mm.sup.2/s
Ethylene-propylene copolymer having kinematic viscosity 5 to 20 wt
% according to JIS K 2283 at 100.degree. C. in the range of from
1000 to 1200 mm.sup.2/s Monocarboxylic acid ester having kinematic
viscosity 5 to 20 wt % according to DIN 51562-1 at 100.degree. C.
in the range of from 2 to 4 mm.sup.2/s Polyalphaolefin 2 5 to 20 wt
%
[0271] Another preferred lubricant composition according to the
present invention as further illustrated by inventive example 5
(IE-5) is defined as follows:
TABLE-US-00009 Lubricant composition Dicarboxylic acid ester
component having dynamic 55-75 wt % viscosity according to DIN
51562-1 at 100.degree. C. in the range of from 12 to 16 mm.sup.2/s
Ethylene-propylene copolymer having kinematic 5 to 20 wt %
viscosity according to JIS K 2283 at 100.degree. C. in the range of
from 1000 to 1200 mm.sup.2/s Monocarboxylic acid ester having
kinematic viscosity 3 to 15 wt % according to DIN 51562-1 at
100.degree. C. in the range of from 2 to 4 mm.sup.2/s
Polyalphaolefin 2 10 to 25 wt % Complex carboxylic acid ester
having kinematic 3 to 15 wt % viscosity according to DIN 51562-1 at
100.degree. C. in the range of from 10 to 20 mm.sup.2/s
[0272] The lubricant compositions according to the present
invention can be used in a variety of different applications.
Preferred embodiments include the use of the lubricant compositions
according to the present invention in light, 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, moulding fluids, gun, pistol and rifle
lubricants or watch lubricants and food grade approved
lubricants.
EXAMPLES
[0273] Methods
[0274] Measurement of the number average molecular weight Mn of
polymers mentioned in the present invention has been carried out
using the industrial standard DIN 55672.
[0275] The pour point of the lubricant compositions according to
the present invention has been determined according to the
established industrial standard DIN ISO 3016 (if not indicated
otherwise).
[0276] The various kinematic viscosities of the lubricant
compositions according to the present invention have been
determined following established industry standards.
[0277] The kinematic viscosity at -30.degree. C., 40.degree. C. and
100.degree. C., respectively, is determined according to the
established industrial standard DIN 51562-1 (unless indicated
otherwise).
[0278] The dynamic viscosity is determined based on DIN 51562-1 and
further calculated by multiplication of the measured kinematic
viscosity with the corresponding density.
[0279] The viscosity index has been determined according to the
industrial standard DIN ISO 2909 (if not indicated otherwise).
[0280] Shear stability testing has been carried out according to
the industrial standard DIN 51350/KRL/C.
[0281] Preparation of Carboxylic Acid Esters
[0282] Preparation of a Diisononyl Adipate (DNA)
[0283] a) Butene Dimerization
[0284] The butene dimerization was carried out continuously in an
adiabatic reactor, composed of two subreactors (length: in each
case 4 m, diameter: in each case 80 cm) with intermediate cooling
at 30 bar. The starting product used was a raffinate II with the
following makeup:
TABLE-US-00010 isobutane 2% by weight n-butane 10% by weight
isobutene 2% by weight 1-butene 32% by weight trans-2-butene 37% by
weight and cis-2-butene 17% by weight.
[0285] The catalyst used was a material prepared in accordance with
DE-A 4339713, composed of 50% by weight of NiO, 12.5% by weight of
TiO.sub.2, 33.5% by weight of SiO.sub.2 and 4% by weight of
Al.sub.2O.sub.3, in the form of 5.times.5 mm tablets. The reaction
was carried out with a throughput of 0.375 kg of raffinate II per I
of catalyst and hour, with a return ratio of unreacted C.sub.4
hydrocarbons returned to fresh raffinate II of 3, an inlet
temperature at the 1st subreactor of 38.degree. C. and an inlet
temperature at the 2nd subreactor of 60.degree. C. The conversion,
based on the butenes present in the raffinate II, was 83.1%, and
the octene selectivity was 83.3%. Fractional distillation of the
reactor discharge was used to separate off the octene fraction from
unreacted raffinate II and from the high-boilers.
[0286] b) Hydroformylation and Hydrogenation
[0287] 750 g of the octene mixture prepared according to section
A.1 of the examples were reacted for 5 hours discontinuously, in an
autoclave, with 0.13% by weight of dicobalt octacarbonyl
Co.sub.2(CO).sub.8 as catalyst, with addition of 75 g of water, at
185.degree. C. and with a synthesis gas pressure of 280 bar at a
ratio of H.sub.2 to CO in the mixture of 60/40. Further material
was injected to make up for the consumption of synthesis gas, seen
in a fall-off of pressure in the autoclave. After releasing the
pressure in the autoclave, the reaction discharge, with 10%
strength by weight acetic acid, was freed oxidatively from the
cobalt catalyst by introducing air, and the organic product phase
was hydrogenated using Raney nickel at 125.degree. C. and with a
hydrogen pressure of 280 bar for 10 h. The isononanol fraction was
separated off from the C.sub.8 paraffins and the highboilers by
fractional distillation of the reaction discharge.
[0288] The composition of the isononanol fraction was analyzed by
gas chromatography. A specimen was trimethylsilylated in advance
using 1 ml of N-methyl-N-trimethylsilyltrifluoracetamide per 100
.mu.l of specimen for 60 minutes at 80.degree. C. Use was made of a
Hewlett Packard Ultra 1 separating column of length 50 m and
internal diameter of 0.32 mm, with a film thickness of 0.2 .mu.m.
Injector temperature and detector temperature were 250.degree. C.,
and the oven temperature was 120.degree. C. The split was 110
ml/min. The carrier gas used was nitrogen. The admission pressure
was set at 200 kPa. 1 .mu.l of the specimen was injected and
detected by FID. The compositions determined for specimens by this
method (percentage by gas chromatogram area) were as follows:
TABLE-US-00011 11.0% 1-nonanol 20.8% 6-methyl-1-octanol 20.5%
4-methyl-1-octanol 5.3% 2-methyl-1-octanol 11.0%
2,5-dimethyl-1-heptanol 8.7% 3-ethyl-1-heptanol 6.2%
4,5-dimethyl-1-heptanol 2.9% 2-ethyl-1-heptanol 2.8%
2,3-dimethyl-1-heptanol 3.0% 2-ethyl-4-methyl-1-hexanol 2.7%
2-propyl-1-hexanol 1.6% 3-ethyl-4-methyl-1-hexanol
[0289] The density of this isononanol mixture was measured at
20.degree. C. as 0.8326, and the refractive index n.sub.D.sup.20 as
1.4353. The boiling range at atmospheric pressure was from 204 to
209.degree. C.
[0290] c) Esterification
[0291] 865.74 g of the isononanol fraction obtained in process step
2 (20% molar excess based on adipic acid) were reacted with 365.25
g of adipic acid and 0.42 g of isopropyl butyl titanate catalyst in
a 2 I autoclave into which nitrogen was bubbled (10 l/h) with a
stirrer speed of 500 rpm and a reaction temperature of 230.degree.
C. The water formed in the reaction was removed progressively from
the reaction mixture with the nitrogen stream. The reaction time
was 180 min. The nonanol excess was then distilled off at a reduced
pressure of 50 mbar. 1000 g of the crude diisononyl adipate were
neutralized by stirring for 10 minutes at 80.degree. C. with 150 ml
of 0.5% strength aqueous sodium hydroxide. This gave a two-phase
mixture with an upper organic phase and a lower aqueous phase
(waste liquor with hydrolyzed catalyst). The aqueous phase was
separated off, and the organic phase subjected to two further
washings with 200 ml of H.sub.2O. For further purification, the
neutralized and washed diisononyl adipate was stripped using steam
at 180.degree. C. and a reduced pressure of 50 mbar for two hours.
The purified diisononyl adipate was then dried for 30 min at
150.degree. C./50 mbar by passing a nitrogen stream (2 l/h) through
the material, then mixed with activated carbon for 5 min and
filtered off with suction via a suction filter using Supra-Theorit
5 filtration aid (temperature 80.degree. C.).
[0292] The resultant diisononyl adipate has a density of 0.920
g/cm.sup.3 and a refractive index n.sub.D.sup.20 of 1.4500.
[0293] Preparation of di-(2-propylheptyl)-phthalate (DPHP)
[0294] Propylheptanol is commercially available from BASF SE,
Ludwigshafen [93.0% by weight 2-propyl-heptanol; 2.9% by weight
2-propyl-4-methyl-hexanol; 3.9% by weight 2-propyl-5-methylhexanol
and 0.2 Gew.-% 2-isopropylheptanol].
[0295] A mixture of structural isomers of an alcohol with 10 carbon
atoms which is available by BASF SE as "propylheptanol" (2.4 mol)
and phthalic acid (1.0 mol) is reacted in the present of
isopropyl-butyl-titanate (0.001 mol) in an autoclave under inert
gas (N.sub.2) at a reaction temperature of 230.degree. C. Water
which is formed during the reaction is removed from the reaction
mixture through an inert gas stream (N.sub.2-stream). After 180
minutes the excess alcohol is removed from the mixture by
distillation at a pressure of 50 mbar. The thus obtained ester is
then neutralized with 0.5% NaOH at 80.degree. C. Afterwards the
organic phase and the aqueous phase are separated, followed by
washing the organic phase two times with water. In a further step
the organic phase is purified by treating the crude ester with
steam at 180.degree. C. and 50 mbar. Then the ester is dried by
subjecting it to a N.sub.2 stream at 150.degree. C. and 50 mbar.
Finally the ester is mixed with activated carbon and is filtered
using as a rheological agent supra-theorit at 80.degree. C. under
reduced pressure. The ester shows a density of 0.962 at 20.degree.
C., measured according to DIN 51757, respectively ASTM D 4052.
[0296] Experimental Tests
Test Example 1
[0297] Shear Stability (KRH Test)
TABLE-US-00012 1E-1 Dicarboxylic ester component DPHA XPB 115 .RTM.
90 wt % Ethylene-propylene copolymer Lucant .TM.HC 2000 10 wt %
1E-1 KRH testing Kinematic Viscosity After 20 h After 100 h at
-30.degree. C. [mm.sup.2/s] 1540 1711 1880 at 40.degree. C.
[mm.sup.2/s] 37.54 36.78 34.44 at 100.degree. C. [mm.sup.2/s] 7.96
7.79 7.32 Viscosity index 192 190 186 Pour point [.degree. C.] -72
-72 -72
[0298] DPHA XPB 115.RTM. (BASF SE) is a di-propylheptyl adipate (a
dicarboxylic acid ester component) having a pourpoint according to
ASTM D97 of <-75.degree. C. and a kinematic viscosity according
to ASTM D445 at 40.degree. C. of 11.56 mm.sup.2/s, at 100.degree.
C. of 3.04 mm.sup.2/s and a viscosity index according to ASTM D2270
of 123;
[0299] Lucant.TM.HC-2000 is an oligomeric ethylene-propylene
copolymer having pour point according to JIS K 2269 of
-10.0.degree. C., kinematic viscosity according to JIS K 2283 at
40.degree. C. of 37500 mm.sup.2/s and at 100.degree. C. of 2000
mm.sup.2/s and viscosity index according to JIS K 2283 of 300.
Test Example 2
[0300] Rheological Profile of Lubricant Compositions at Different
Temperatures
TABLE-US-00013 IE-2 1E-3 1E-4 1E-5 Dicarboxylic ester Plastomoll
.RTM. DOA Plastomoll .RTM. DOA Plastomoll .RTM. DOA Plastomoll
.RTM. DOA component 70.00 wt % 68.00 wt % 63.50 wt % 63.00 wt %
Ethylene- Lucant .TM.HC 1100 Lucant .TM.HC 1100 Lucant .TM.HC 1100
Lucant .TM.HC 1100 propylene copolymer 12.00 wt % 12.00 wt % 12.50
wt % 12.00 wt % Monoester component Synative ES EHO Synative ES EHO
Synative ES EHO Synative ES EHO 18.00 wt % 8.00 wt % 9.00 wt % 7.00
wt % Base oil PAO-2 PAO-2 PAO-2 12.00 wt % 15.00 wt % 13.00 wt %
Complex ester Synative ES 3345 5.00 wt % Kinematic Viscosity at
-30.degree. C. [mm.sup.2/s] 903 1006 1535 1200 at 40.degree. C.
[mm.sup.2/s] 37.67 31.90 32.7 33.76 at 100.degree. C. [mm.sup.2/s]
8.73 7.62 7.81 7.90 Viscosity index 222 221 222 219 Pour point
[.degree. C.] n.d. -72 n.d. n.d.
[0301] Plastomoll.RTM. DOA (BASF SE) is a di-(2-ethylhexyl)adipate
(a dicarboxylic acid ester component) having a pourpoint according
to DIN ISO 3016 of <-60.degree. C. and a dynamic viscosity
according to DIN 51562 at 20.degree. C. of 13-15 mPas;
[0302] Lucant.TM.HC-1100 is an oligomeric ethylene-propylene
copolymer having pour point according to JIS K 2269 of
-12.5.degree. C., kinematic viscosity according to JIS K 2283 at
40.degree. C. of 18900 mm.sup.2/s and at 100.degree. C. of 1100
mm.sup.2/s and viscosity index according to JIS K 2283 of 270;
[0303] Synative ES EHO.RTM. (BASF SE) is 2-ethylhexyloleate (a
monocarboxylic acid ester) having a pourpoint according to DIN ISO
3016 of not higher than -30.degree. C.;
[0304] Synative ES 3345.RTM. (BASF SE) is a complex carboxylic acid
ester component having a pourpoint according to DIN ISO 3016 of not
higher than -40.degree. C., a kinematic viscosity according to DIN
51562.1 at 40.degree. C. in the range of 105 to 120 mm.sup.2/s, at
100.degree. C. in the range of 13 to 18 mm.sup.2/s and a viscosity
index according to DIN ISO 2090 in the range of from 140 to 160
mm.sup.2/s.
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