U.S. patent application number 14/443769 was filed with the patent office on 2015-10-29 for use of polyesters as lubricants.
The applicant listed for this patent is BASF SE. Invention is credited to Boris Breitscheidel, Markus Scherer.
Application Number | 20150307807 14/443769 |
Document ID | / |
Family ID | 47257510 |
Filed Date | 2015-10-29 |
United States Patent
Application |
20150307807 |
Kind Code |
A1 |
Scherer; Markus ; et
al. |
October 29, 2015 |
Use Of Polyesters As Lubricants
Abstract
The presently claimed invention is directed to the novel use of
polyester obtainable by reacting a mixture comprising
cyclohexane-1,2-dicarboxylic acid and an alcohol mixture comprising
1-nonanol, monomethyloctanols, dimethylheptanols and
monoethylheptanols and subsequent hydrogenation of said total
mixture as lubricants and a lubricant composition comprising these
polyesters.
Inventors: |
Scherer; Markus; (Mannheim,
DE) ; Breitscheidel; Boris; (Waldsee, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
BASF SE |
Ludwigshafen |
|
DE |
|
|
Family ID: |
47257510 |
Appl. No.: |
14/443769 |
Filed: |
November 5, 2013 |
PCT Filed: |
November 5, 2013 |
PCT NO: |
PCT/EP2013/073074 |
371 Date: |
May 19, 2015 |
Current U.S.
Class: |
508/482 |
Current CPC
Class: |
C10M 2205/026 20130101;
C10M 2203/1025 20130101; C10M 2205/0285 20130101; C10M 2207/285
20130101; C10M 2205/173 20130101; C10N 2020/02 20130101; C10M
169/047 20130101; C10N 2030/02 20130101; C10M 129/72 20130101; C10M
2207/285 20130101; C10N 2060/02 20130101; C10M 2203/1025 20130101;
C10N 2020/02 20130101; C10M 2203/1025 20130101; C10N 2020/02
20130101; C10M 2207/285 20130101; C10N 2060/02 20130101 |
International
Class: |
C10M 169/04 20060101
C10M169/04 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 19, 2012 |
EP |
12193151.3 |
Claims
1. Use of a polyester obtainable by reacting a total mixture
comprising phthalic acid, optionally in form of its esters or its
anhydrides, and an alcohol mixture comprising 1-nonanol,
monomethyloctanols, dimethylheptanols and monoethylheptanols and
subsequent hydrogenation of said total mixture, whereby the
polyester has a dynamic viscosity at 20.degree. C. in the range of
40 to 64 mPas determined according to DIN 51562-1, as
lubricant.
2. The use according to claim 1, characterized in that the
polyester has a dynamic viscosity at 20.degree. C. in the range of
42 to 62 mPas determined according to DIN 51562.
3. The use according to claim 1 or 2, characterized in that the
alcohol mixture contains a proportion of 25% by weight to 55% by
weight monomethyloctanols, related to the overall weight of the
alcohol mixture.
4. The use according to one or more of claims 1 to 3, characterized
in that the alcohol mixture contains a proportion of 10% by weight
to 30% by weight dimethylheptanols, related to the overall weight
of the alcohol mixture.
5. The use according to one or more of claims 1 to 4, characterized
in that 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.
6. The use according to one or more of claims 1 to 5, characterized
in that the alcohol mixture is present in a molar ratio in the
range of 1:1 to 2:1 in relation to phthalic acid, optionally in
form of its esters or its anhydrides.
7. A lubricant composition comprising A) at least one lubricating
base oil, B) at least one polyester obtainable by reacting a total
mixture comprising phthalic acid, optionally in form of its esters
or its anhydrides, and an alcohol mixture comprising 1-nonanol,
monomethyloctanols, dimethylheptanols and monoethylheptanols and
subsequent hydrogenation of said total mixture, whereby the
polyester has a dynamic viscosity at 20.degree. C. in the range of
40 to 62 mPas determined according to DIN 51562-1 and C)
lubricating oil additives.
8. The lubricant composition according to claim 7, characterized in
that the lubricating base oil is hydrorefined mineral oil and/or
synthetic hydrocarbon oil.
9. The lubricant composition according to claim 8, characterized in
that the hydrorefined mineral oil is selected from the group
consisting of hydrorefined naphthenic mineral oil, API base oil
classification Group II and Group III hydrorefined paraffinic
mineral oil.
10. The lubricant composition according to claim 8, characterized
in that the synthetic hydrocarbon oil is selected from the group
consisting of isoparaffinic synthetic oil, GTL synthetic oil and
poly-.alpha.-olefin (PAO) belonging to API base oil classification
Group IV.
11. The lubricant composition according to one or more of claims 7
to 10, characterized in that the polyester has a dynamic viscosity
at 20 .degree. C. in the range of 42 to 61 mPas determined
according to DIN 51562-1.
12. The lubricant composition according to one or more of claims 7
to 11, characterized in that the alcohol mixture contains a
proportion of 25% by weight to 55% by weight monomethyloctanols,
related to the overall weight of the alcohol mixture.
13. The lubricant composition according to one or more of claims 7
to 12, characterized in that the alcohol mixture contains a
proportion of 10% by weight to 30% by weight dimethylheptanols,
related to the overall weight of the alcohol mixture.
14. The lubricant composition according to one or more of claims 7
to 13, characterized in that 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.
15. The lubricant composition according to claim 7, characterized
in that the lubricating oil additives are selected from the group
consisting of lubricity improvers, viscosity improvers, combustion
improvers, corrosion and/or oxidation inhibiting agents, pour point
depressing agents, extreme pressure agents, antiwear agents,
antifoam agents, detergents, dispersants, antioxidants and metal
passivators.
Description
[0001] The presently claimed invention is directed to the novel use
of polyester obtainable by reacting a mixture comprising
cyclohexane-1,2-dicarboxylic acid and an alcohol mixture comprising
1-nonanol, monomethyloctanols, dimethylheptanols and
monoethylheptanols as lubricants and subsequent hydrogenation of
said total mixture and a lubricant composition comprising these
polyesters.
[0002] The commercially available lubricant compositions are
produced from a multitude of different natural or synthetic
components. The lubricant compositions comprise base oils and
further additives. The base oils often consist of mineral oils,
highly refined mineral oils, alkylated mineral oils,
poly-alpha-olefins (PAOs), polyalkylene glycols, phosphate esters,
silicone oils, diesters and esters of polyhydric alcohols.
[0003] Currently Group II and Group III hydrorefined paraffinic
mineral oil, GTL synthetic oil and poly-.alpha.-olefin are
preferably used as base oil in lubricant compositions. However,
these base oils have a detrimental effect on sealing materials
which form a part of engines and mechanical transmission units. In
particular, the use of these base oils leads to the shrinkage of
sealing materials such as acrylonitrile butadiene rubber.
[0004] It is known that polyesters, however, accelerate the
expansion of these sealing materials. Thus, specific polyesters are
used in lubricant compositions in order to counteract the shrinking
effect of modern base oils.
[0005] At present, DIDA (diisodecyl adipate), DITA (diisotridecyl
adipate) and TMTC (trimethylolpropanolcaprylate) are used to
achieve this purpose. The cloud points of these esters lie at
-30.degree. C., -20.degree. C. and -10.degree. C.,
respectively.
[0006] In view of the properties of existing polyesters there is
still a need to provide novel polyesters that show improved low
temperature properties as expressed by low cloud points while
maintaining overall advantageous characteristics of lubricant
formulations such as expansions of sealing materials such as
acrylonitrile butadiene rubber, when used as a component of a
lubricant composition.
[0007] Thus, it is an object of the present invention to provide
polyesters that show improved low temperature properties as
expressed by low cloud points and lead to a high degree of
expansion of sealing materials such as acrylonitrile butadiene
rubber when used as a component of a lubricant composition.
[0008] The object is solved by means of using a polyester
obtainable by reacting a total mixture comprising phthalic acid,
optionally in form of its esters or its anhydrides, and an alcohol
mixture comprising 1-nonanol, monomethyloctanols, dimethylheptanols
and monoethylheptanols and subsequent hydrogenation of said total
mixture, whereby the polyester has a dynamic viscosity at
20.degree. C. in the range of 40 to 64 mPas determined according to
DIN 51562-1, as a lubricant.
[0009] The dynamic viscosity of the polyester at 20.degree. C. is
preferably from 42 to 62 mPas, more preferably from 44 to 60 mPas
determined according to DIN 51562-1.
[0010] The polyesters of the invention preferably have densities at
20.degree. C. according to DIN 51757 of from 0.85 to 1.00
g/cm.sup.3, more preferably from 0.90 to 0.98 g/cm.sup.3 and most
preferably from 0.94 to 0.96 g/cm.sup.3. The refractive index
n.sub.D.sup.20 according to DIN 51423 is preferably from 1.455 to
1.469, more preferably from 1.456 to 1.468, and most preferably
from 1.460 to 1.466.
[0011] The alcohol mixture used according to the invention 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.9aldehydes 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.
[0012] 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 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.
[0013] 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-00001 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.
[0014] 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.
[0015] 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.
[0016] 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.
[0017] 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. 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.
[0018] 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.
[0019] 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.
[0020] 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.
[0021] For the purposes of the present invention, 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.
[0022] 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.
[0023] 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.
[0024] 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.
[0025] 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 kieselguhr. It
is also possible to use catalysts comprising noble metals, such as
platinum or palladium.
[0026] 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.
[0027] 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.
[0028] 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):
[0029] The proportion of 1-nonanol in the alcohol mixture of the
invention 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.
[0030] 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.
[0031] 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.
[0032] The alcohol mixture of the invention is preferably composed
of from 70 to 100%, more preferably from 70 to 98%, 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.
[0033] 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.
[0034] 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 phthalic acid, optionally in
form of its esters or its anhydrides.
[0035] Preferably the alcohol mixture contains a proportion of 6.0
to 16.0% by weight, preferably 7.0 to 15.0% by weight, particularly
preferably 8.0 to 14.0% by weight, of n-nonanol; 12.8 to 28.8% by
weight, preferably 14.8 to 26.8% by weight, particularly preferably
15,8 to 25.8% by weight, of 6-methyloctanol; 12.5 to 28.8% by
weight, preferably 14.5 to 26.5% by weight, particularly preferably
15.5 to 25.5% by weight, of 4-methyloctanol; 3.3 to 7.3% by weight,
preferably 3.8 to 6.8% by weight, particularly preferably 4.3 to
6.3% by weight, of 2-methyloctanol; 5.7 to 11.7% by weight,
preferably 6.3 to 11.3% by weight, particularly preferably 6.7 to
10.7% by weight, of 3-ethylheptanol; 1.9 to 3.9% by weight,
preferably 2.1 to 3.7% by weight, particularly preferably 2.4 to
3.4% by weight, of 2-ethylheptanol; 1.7 to 3.7% by weight,
preferably 1.9 to 3.5% by weight, particularly preferably 2.2 to
3.2% by weight, of 2-propylhexanol; 3.2 to 9.2% by weight,
preferably 3.7 to 8.7% by weight, particularly preferably 4.2 to
8.2% by weight, of 3,5-dimethylheptanol; 6.0 to 16.0% by weight,
preferably 7.0 to 15.0% by weight, particularly preferably 8.0 to
14.0% by weight, of 2,5-dimethylheptanol; 1.8 to 3.8% by weight,
preferably 2.0 to 3.6% by weight, particularly preferably 2.3 to
3.3% by weight, of 2,3-dimethylheptanol; 0.6 to 2.6% by weight,
preferably 0.8 to 2.4% by weight, particularly preferably 1.1 to
2.1% by weight, of 3-ethyl-4-methylhexanol; 2.0 to 4.0% by weight,
preferably 2.2 to 3.8% by weight, particularly preferably 2.5 to
3.5% by weight, of 2-ethyl-4-methylhexanol; 0.5 to 6.5% by weight,
preferably 1.5 to 6% by weight, particularly preferably 1.5 to 5.5%
by weight, of other alcohols having 9 carbon atoms; the total sum
of said components being 100% by weight.
[0036] 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. The refractive index n D.sup.2.degree. 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.
[0037] The preparation of the polyesters of the invention is
carried out in a manner known per se (cf., for example, "Ullmann's
Encyclopedia of Industrial Chemistry", 5th edition, VCH
Verlagsgesellschaft mbH, Weinheim, Vol. A1, pp. 214 et seq. and
Vol. A9, pp. 572-575). The chain length and, respectively, average
molecular weight of the polyesters can be controlled via the
juncture at which the alcohol mixture is added and the amount of
this mixture, and these may readily be determined as a matter of
routine by the skilled worker. The catalysts used comprise
conventional esterification catalysts, preferably dialkyl titanates
((RO).sub.2TiO.sub.2, where examples of R are iso-propyl, n-butyl
and isobutyl), methanesulfonic acid and sulfuric acid, more
preferably the catalyst is isopropyl-n-butyl titanate.
[0038] In one preferred embodiment, the initial charge in the
reaction vessel comprises phthalic acid and the entire amount of
the alcohol mixture. This reaction mixture is first heated to
100-140.degree. C. and homogenized by stirring. Heating then
continues to 160-190 .degree. C. at atmospheric pressure. The
esterification, with elimination of water, preferably begins at
about 150.degree. C. The water of reaction formed is removed by
distillation via a column. If the alcohol mixture distills over
during this procedure, it is returned to the reaction vessel. The
reaction vessel is then heated to 200-250.degree. C., and further
water of reaction is stripped at a pressure of from 150 to 300
mbar, by passing nitrogen through the reaction mixture. Residual
water and excess alcohol mixture are stripped here, using an
increased flow of nitrogen and stirring. The reaction mixture is
then filtered at 100-140.degree. C.
[0039] Preferably hydrogenation of the total mixture is carried out
with a gas comprising hydrogen in the presence of a catalyst which
comprises, as active metal, at least one metal of subgroup VIII of
the Periodic Table of the Elements, alone or together with at least
one metal of subgroup I or VII of the Periodic Table of the
Elements, applied to a support, the support having macropores.
[0040] In a preferred embodiment, the support has a mean pore
diameter of at least 50 nm and a BET surface area of not more than
30 m.sup.2/g and the amount of the active metal is 0,01 to 30% by
weight, based on the total weight of the catalyst.
[0041] In a further embodiment, a catalyst is used in which the
amount of the active metal is 0.01 to 30% by weight, based on the
total weight of the catalyst, and 10 to 50% of the pore volume of
the support is formed by macropores having a pore diameter in the
range of 50 nm to 10 000 nm and 50 to 90% of the pore volume of the
support is formed by mesopores having a pore diameter in the range
of 2 to 50 nm, the sum of the proportions of pore volumes being
100%.
[0042] In a further embodiment, the catalyst has 0.01 to 30% by
weight, based on the total weight of the catalyst, of an active
metal, applied to a support, the support having a mean pore
diameter of at least 0.1 .mu.m and a BET surface area of not more
than 15 m.sup.2/g. Supports which may be used are in principle all
supports which have macropores, i.e. supports which have
exclusively macropores and those which also comprise mesopores
and/or micropores in addition to macropores.
[0043] In principle, all metals of subgroup VIII of the Periodic
Table of the Elements can be used as active metal. Platinum,
rhodium, palladium, cobalt, nickel or ruthenium or a mixture of two
or more thereof is preferably used as active metals, in particular
ruthenium being used as active metal. Among the metals of subgroup
I or VII or of subgroup I and VII of the Periodic Table of the
Elements, all of which can in principle likewise be used, copper
and/or rhenium are preferably employed.
[0044] In the context of the present application, the terms
"macropores" and "mesopores" are used in the manner defined in Pure
Appl. Chem., 45, page 79 (1976), namely as pores whose diameter is
above 50 nm (macropores) or whose diameter is between 2 nm and 50
nm (mesopores).
[0045] The content of the active metal is in general 0.01 to 30% by
weight, preferably 0.01 to 5% by weight, particularly preferably
0.1 to 5% by weight, based in each case on the total weight of the
catalyst used.
[0046] The polyester of the presently claimed invention can be used
as a lubricant in industrial oils. Industrial oils can be selected
from the group consisting of light, medium and heavy duty engine
oils, industrial engine oils, marine 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, drilling detergents for the
soil exploration, hydraulic oils, chain saw oil and gun, pistol and
rifle lubricants.
[0047] The industrial oil may preferably comprises further
additives such as polymer thickeners, viscosity index improvers,
antioxidants, corrosion inhibitors, detergents, dispersants,
demulsifiers, defoamers, dyes, wear protection additives, EP
(extreme pressure) additives, AW (antiwear) additives and friction
modifiers.
[0048] Further the industrial oil may comprise other base oils
and/or co-solvents like mineral oils (Gr I, II or III oils),
polyalphaolefins, alkyl naphthalenes, mineral oil soluble
polyalkylene glycols, silicone oils, phosphate esters and/or other
carboxylic acid esters.
[0049] Typical additives found in hydraulic oils include
dispersants, detergents, corrosion inhibitors, antiwear agents,
antifoamants, friction modifiers, seal swell agents, demulsifiers,
VI improvers, and pour point depressants.
[0050] Examples of dispersants include polyisobutylene
succinimides, polyisobutylene succinate esters and Mannich Base
ashless dispersants.
[0051] Examples of detergents include metallic alkyl phenates,
sulfurized metallic alkyl phenates, metallic alkyl sulfonates and
metallic alkyl salicylates.
[0052] Examples of anti-wear additives include organo borates,
organo phosphites, organic sulfur-containing compounds, zinc
dialkyl dithiophosphates, zinc diaryl dithiophosphates and
phosphosulfurized hydrocarbons.
[0053] Examples of friction modifiers include fatty acid esters and
amides, organo molybdenum compounds, molybdenum
dialkylthiocarbamates and molybdenum dialkyl dithiophosphates.
[0054] An example of an antifoamant is polysiloxane. Examples of
rust inhibitors are polyoxyalkylene polyols, carboxylic acids or
triazol components. Examples of VI improvers include olefin
copolymers, polyalkylmethacrylates and dispersant olefin
copolymers. An example of a pour point depressant is
polyalkylmethacrylate.
[0055] The polyester of the presently claimed invention can be used
as a lubricant in metalworking fluids.
[0056] Depending on the applications, e.g., straight oils (neat
oils) or soluble oils, the metalworking fluid may contain
applicable additives known in the art to improve the properties of
the composition in amounts ranging from 0.10 to 40 wt. %. These
additives include metal deactivators; corrosion inhibitors;
antimicrobial; anticorrosion; emulsifying agents; couplers; extreme
pressure agents; antifriction; antirust agents; polymeric
substances; anti-inflammatory agents; bactericides; antiseptics;
antioxidants; chelating agents; pH regulators; antiwear agents
including active sulphur anti-wear additive packages; a
metalworking fluid additive package containing at least one of the
aforementioned additives.
[0057] Depending on the end-use applications, small quantities of
additives such as anti-misting agents may be optionally added in an
amount ranging from 0.05 to 5.0% by vol. in one embodiment and less
than 1 wt. % in other embodiments. Non-limiting examples include
rhamsan gum, hydrophobic and hydrophilic monomers, styrene or
hydrocarbyl-substituted styrene hydrophobic monomers and
hydrophilic monomers, oil soluble organic polymers ranging in
molecular weight (viscosity average molecular weight) from about
0.3 to over 4 million such as isobutylene, styrene, alkyl
methacrylate, ethylene, propylene, n-butylene vinyl acetate, etc.
In one embodiment, polymethylmethacrylate or poly(ethylene,
propylene, butylene or isobutylene) in the molecular weight range 1
to 3 million is used.
[0058] For certain applications, a small amount of foam inhibitors
in the prior art can also be added to the composition in an amount
ranging from 0.02 to 15.0 wt. %. Non-limiting examples include
polydimethylsiloxanes, often trimethylsilyl terminated, alkyl
polymethacrylates, polymethylsiloxanes, an N-acylamino acid having
a long chain acyl group and/or a salt thereof, an N-alkylamino acid
having a long chain alkyl group and/or a salt thereof used
concurrently with an alkyl-alkylene oxide and/or an acylalkylene
oxide, acetylene diols and ethoxylated acetylene diols, silicones,
hydrophobic materials (e.g. silica), fatty amides, fatty acids,
fatty acid esters, and/or organic polymers, modified siloxanes,
polyglycols, esterified or modified polyglycols, polyacrylates,
fatty acids, fatty acid esters, fatty alcohols, fatty alcohol
esters, oxo-alcohols, fluorosurfactants, waxes such as
ethylenebisstereamide wax, polyethylene wax, polypropylene wax,
ethylenebisstereamide wax, and paraffinic wax. The foam control
agents can be used with suitable dispersants and emulsifiers.
Additional active foam control agents are described in "Foam
Control Agents", by Henry T. Kemer (Noyes Data Corporation, 1976),
pages 125-162.
[0059] The metalworking fluid further comprises anti-friction
agents including overbased sulfonates, sulfurized olefins,
chlorinated paraffins and olefins, sulfurized ester olefins, amine
terminated polyglycols, and sodium dioctyl phosphate salts. In yet
other embodiment, the composition further comprises corrosion
inhibitors including carboxylic/boric acid diamine salts,
carboxylic acid amine salts, alkanol amines and alkanol amine
borates.
[0060] The metalworking fluid further comprises oil soluble metal
deactivators in an amount of 0.01 to 0.5 vol % (based on the final
oil volume). Non-limiting examples include triazoles or
thiadiazoles, specifically aryl triazoles such as benzotriazole and
tolyltriazole, alkyl derivatives of such triazoles, and
benzothiadiazoles such as R(C.sub.6H.sub.3)N.sub.2S where R is H or
C.sub.1 to C.sub.10 alkyl.
[0061] A small amount of at least an antioxidant in the range 0.01
to 1.0 weight % can be added. Non-limiting examples include
antioxidants of the aminic or phenolic type or mixtures thereof,
e.g., butylated hydroxy toluene (BHT), bis-2,6-di-t-butylphenol
derivatives, sulfur containing hindered phenols, and sulfur
containing hindered bisphenol.
[0062] The metalworking fluid further comprises 0.1 to 20 wt. % of
at least an extreme-pressure agent. Non-limiting examples of
extreme pressure agents include zinc dithiophosphate, molybdenum
oxysulfide dithiophosphate, molybdenum amine compounds, sulfurized
oils and fats, sulfurized fatty acids, sulfurized esters,
sulfurized olefins, dihydrocarbyl polysulfides, thiocarbamates,
thioterpenes and dialkyl thiodipropionates.
[0063] In another embodiment, the presently claimed invention is
related to a lubricant composition comprising [0064] A) at least
one lubricating base oil, [0065] B) at least one polyester
obtainable by reacting a total mixture comprising phthalic acid,
optionally in form of its esters or its anhydrides, and an alcohol
mixture comprising 1-nonanol, monomethyloctanols, dimethylheptanols
and monoethylheptanols and subsequent hydrogenation of said total
mixture, whereby the polyester has a dynamic viscosity at
20.degree. C. in the range of 40 to 62 mPas determined according to
DIN 51562-1 and [0066] C) lubricating oil additives.
[0067] For the sake of conciseness, any preferred embodiment that
refers to the use of the inventively claimed polyester also refers
to the lubricant composition itself.
[0068] Preferably the lubricant composition comprises 0,1% by
weight to 50% by weight of component A), 50% by weight to 90% by
weight of component B) and 0,1% by weight to 40% by weight of
component C).
[0069] In another embodiment, the lubricant composition preferably
comprises 30% by weight to 90% by weight of component A), 0.1% by
weight to 50% by weight of component B) and 0.1% by weight to 40%
by weight of component C).
[0070] More preferably the lubricant composition comprises 50% by
weight to 90% by weight of component A), 3.5% by weight to 45% by
weight of component B) and 1,0% by weight to 30% by weight of
component C).
[0071] Most preferably the lubricant composition comprises 60% by
weight to 90% by weight of component A), 10% by weight to 25% by
weight of component B) and 2.0% by weight to 20% by weight of
component C).
[0072] The viscosity of the lubricant composition at 40.degree. C.
is preferably from 60 to 140 mm.sup.2/s, more preferably from 70 to
130 mm.sup.2/s and most preferably from 80 to 120 mm.sup.2/s
determined according to DIN 51562-1.
[0073] Preferably the lubricating base oil is hydrorefined mineral
oil and/or synthetic hydrocarbon oil. Preferably the hydrorefined
mineral oil is selected from the group consisting of hydrorefined
naphthenic mineral oil, API base oil classification Group II and
Group III hydrorefined paraffinic mineral oil. Preferably the
synthetic hydrocarbon oil is selected from the group consisting of
isoparaffinic synthetic oil, GTL synthetic oil and
poly-.alpha.-olefin (PAO) belonging to API base oil classification
Group IV.
[0074] Preferably the lubricating oil additives are selected from
the group consisting of lubricity improvers, viscosity improvers,
combustion improvers, corrosion and/or oxidation inhibiting agents,
pour point depressing agents, extreme pressure agents, antiwear
agents, antifoam agents, detergents, dispersants, antioxidants and
metal passivators.
[0075] Typical lubricity improvers are commercial acid-based
lubricity improvers which have fatty acids as their main
constituent and ester-based lubricity improvers which have as their
main constituent glycerin mono fatty acid esters. These compounds
may be used singly or in combinations of two or more kinds. The
fatty acids used in these lubricity improvers are preferably those
that have as their main constituent a mixture of unsaturated fatty
acids of approximately 12 to 22 carbons, but preferably about 18
carbons, that is oleic acid, linolic acid and linolenic acid.
[0076] Viscosity improvers include but are not limited to
polyisobutenes, polymethyacrylate acid esters, polyacrylate acid
esters, diene polymers, polyalkyl styrenes, alkenyl aryl conjugated
diene copolymers, polyolefins and multifunctional viscosity
improvers.
[0077] Pour point depressing agents are a particularly useful type
of additive, often included in the lubricating oils described
herein, usually comprising substances such as polymethacrylates,
styrene-based polymers, crosslinked alkyl phenols, or alkyl
naphthalenes. See for example, page 8 of "Lubricant Additives" by
C. V. Smalheer and R. Kennedy Smith (Lesius-Hiles Company
Publishers, Cleveland, Ohio, 1967).
[0078] For instance, corrosion inhibiting agents, extreme pressure
agents, and antiwear agents include but are not limited to
dithiophosphoric esters; chlorinated aliphatic hydrocarbons;
boron-containing compounds including borate esters and molybdenum
compounds.
[0079] Antifoam agents used to reduce or prevent the formation of
stable foam include silicones or organic polymers. Examples of
these and additional antifoam compositions are described in "Foam
Control Agents", by Henry T. Kerner (Noyes Data Corporation, 1976),
pages 125-162. Additional antioxidants can also be included,
typically of the aromatic amine or hindered phenol type. These and
other additives which may be used in combination with the present
invention are described in greater detail in U.S. Pat. No.
4,582,618 (column 14, line 52 through column 17, line 16,
inclusive).
[0080] Dispersants are well known in the field of lubricants and
include primarily what are sometimes referred to as "ashless"
dispersants because (prior to mixing in a lubricating composition)
they do not contain ash-forming metals and they do not normally
contribute any ash forming metals when added to a lubricant
composition. Dispersants are characterized by a polar group
attached to a relatively high molecular weight hydrocarbon
chain.
[0081] One class of dispersant is Mannich bases. These are
materials which are formed by the condensation of a higher
molecular weight, alkyl substituted phenol, an alkylene polyamine,
and an aldehyde such as formaldehyde and are described in more
detail in U.S. Pat. No. 3,634,515. Another class of dispersant is
high molecular weight esters. These materials are similar to
Mannich dispersants or the succinimides described below, except
that they may be seen as having been prepared by reaction of a
hydrocarbyl acylating agent and a polyhydric aliphatic alcohol such
as glycerol, pentaerythritol, or sorbitol. Such materials are
described in more detail in U.S. Pat. No. 3,381,022. Other
dispersants include polymeric dispersant additives, which are
generally hydrocarbon-based polymers.
[0082] A preferred class of dispersants is the carboxylic
dispersants. Carboxylic dispersants include succinic-based
dispersants, which are the reaction product of a hydrocarbyl
substituted succinic acylating agent with an organic hydroxy
compound or, in certain embodiments, an amine containing at least
one hydrogen attached to a nitrogen atom, or a mixture of said
hydroxy compound and amine. The term "succinic acylating agent"
refers to a hydrocarbon-substituted succinic acid or succinic
acid-producing compound. Such materials typically include
hydrocarbyl-substituted succinic acids, anhydrides, esters
(including half esters) and halides. Succinimide dispersants are
more fully described in U.S. Pat. Nos. 4,234,435 and 3,172,892.
[0083] The amines which are reacted with the succinic acylating
agents to form the carboxylic dispersant composition can be
monoamines or polyamines. Polyamines include principally alkylene
polyamines such as ethylene polyamines (i.e.,
poly(ethyleneamine)s), such as ethylene diamine, triethylene
tetramine, propylene diamine, decamethylene diamine, octamethylene
diamine, di(heptamethylene) triamine, tripropylene tetramine,
tetraethylene pentamine, trimethylene diamine, pentaethylene
hexamine, di(-trimethylene)triamine. Higher homologues such as are
obtained by condensing two or more of the above-illustrated
alkylene amines like-wise are useful. Tetraethylene pentamines is
particularly useful.
[0084] Hydroxyalkyl-substituted alkylene amines, i.e., alkylene
amines having one or more hydroxyalkyl substituents on the nitrogen
atoms, likewise are useful, as are higher homologues obtained by
condensation of the above-illustrated alkylene amines or hydroxy
alkyl-substituted alkylene amines through amino radicals or through
hydroxy radicals.
[0085] The dispersants may be borated materials. Borated
dispersants are well-known materials and can be prepared by
treatment with a borating agent such as boric acid. Typical
conditions include heating the dispersant with boric acid at 100 to
150.degree. C.
[0086] The amount of the dispersant in a lubricant composition, if
present, will typically be 0.5 to 10 percent by weight, or 1 to 8
percent by weight, or 3 to 7 percent by weight. Its concentration
in a concentrate will be correspondingly increased, to, e.g., 5 to
80 weight percent.
[0087] Detergents are generally salts of organic acids, which are
often overbased. Metal overbased salts of organic acids are widely
known to those of skill in the art and generally include metal
salts wherein the amount of metal present exceeds the
stoichiometric amount. Such salts are said to have conversion
levels in excess of 100% (i.e., they comprise more than 100% of the
theoretical amount of metal needed to convert the acid to its
"normal" or "neutral" salt). They are commonly referred to as
overbased, hyperbased or superbased salts and are usually salts of
organic sulfur acids, organic phosphorus acids, carboxylic acids,
phenols or mixtures of two or more of any of these. As a skilled
worker would realize, mixtures of such overbased salts can also be
used.
[0088] The overbased compositions can be prepared based on a
variety of well-known organic acidic materials including sulfonic
acids, carboxylic acids (including substituted salicylic acids),
phenols, phosphonic acids, saligenins, salixarates, and mixtures of
any two or more of these.
[0089] The basically reacting metal compounds used to make these
overbased salts are usually an alkali or alkaline earth metal
compound, although other basically reacting metal compounds can be
used. Compounds of Ca, Ba, Mg, Na and Li, such as their hydroxides
and alkoxides of lower alkanols are usually used. Overbased salts
containing a mixture of ions of two or more of these metals can be
used.
[0090] Overbased materials are generally prepared by reacting an
acidic material (typically an inorganic acid or lower carboxylic
acid, such as carbon dioxide) with a mixture comprising an acidic
organic compound, a reaction medium comprising at least one inert,
organic solvent (mineral oil, naphtha, toluene, xylene, etc.) for
said acidic organic material, a stoichiometric excess of a metal
base, and a promoter.
[0091] The acidic material used in preparing the overbased material
can be a liquid such as formic acid, acetic acid, nitric acid, or
sulfuric acid. Acetic acid is particularly useful. Inorganic acidic
materials can also be used, such as HCl, SO.sub.2, SO.sub.3,
CO.sub.2, or H.sub.2S, e.g., CO.sub.2 or mixtures thereof, e.g.,
mixtures of CO.sub.2 and acetic acid.
[0092] The detergents generally can also be borated by treatment
with a borating agent such as boric acid. Typical conditions
include heating the detergent with boric acid at 100 to 150.degree.
C., the number of equivalents of boric acid being roughly equal to
the number of equivalents of metal in the salt.
[0093] The amount of the detergent component in a lubricant
composition, if present, will typically be 0.5 to 10 percent by
weight, such as 1 to 7 percent by weight, or 1.2 to 4 percent by
weight. Its concentration in a concentrate will be correspondingly
increased, to, e.g., 5 to 65 weight percent.
[0094] Examples of metal passivators include, but are not limited
to, tolyltriazole and its derivatives, and benzotriazole and its
derivatives. When used, the metal passivators are typically present
in the fluid composition in an amount of from 0.05 to 5, more
typically from 0.05 to 2, parts by weight based on the total weight
of the fluid composition.
[0095] The examples below illustrate the invention in further
detail without being limiting.
EXAMPLES
[0096] A) Preparation of a Polyester of the Invention
[0097] A.1) Butene Dimerization
[0098] 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-00002 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.
[0099] 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.
[0100] A.2) Hydroformylation and Hydrogenation
[0101] 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 Cs paraffins and the high-boilers by
fractional distillation of the reaction discharge.
[0102] 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-00003 11.0% 1-nonanol 20.8% 6-methyl-1-octanol 20.5%
4-methyl-1-octanol 5.3% 2-meth-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
[0103] 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.
[0104] A.3) Esterification
[0105] Viscosity Measurement
[0106] The viscosity of the esters is determined in a standard test
according to DIN 51562-1.
[0107] In the third process step, 865.74 g of the isononanol
fraction obtained in process step 2 (20% excess based on phthalic
anhydride) were reacted with 370.30 g of phthalic anhydride and
0.42 g of isopropyl butyl titanate as catalyst in a 2 l autoclave
with N.sub.2 sparging (10 l/h) with a stirring speed of 500 rpm and
a reaction temperature of 230.degree. C. The water of reaction
formed was removed continuously from the reaction mixture with the
N.sub.2 stream. The reaction time was 180 minutes. The isononanol
excess was subsequently distilled off under a reduced pressure of
50 mbar. 1000 g of the crude polyester were neutralized with 150 ml
of 0.5% strength aqueous sodium hydroxide solution, by stirring at
80.degree. C. for 10 minutes. This gave a two-phase mixture having
an upper organic phase and a lower aqueous phase (waste liquor
comprising hydrolyzed catalyst). The aqueous phase was removed and
the organic phase was washed with twice 200 ml of H2O. For further
purification, the neutralized and washed polyester was stripped
with steam at 180.degree. C. and a reduced pressure of 50 mbar for
2 hours. The purified polyester was then dried at 150.degree. C./50
mbar for 30 minutes by passage of an N.sub.2 stream (2 l/h), then
stirred with activated carbon for 5 minutes, and filtered off on a
suction filter with Supra-Theorit 5 filter aid (temperature
80.degree. C.).
[0108] The resultant polyester possesses a density of 0.973
g/cm.sup.3, a viscosity of 73.0 mPa*s and a refractive index
n.sub.D.sup.20 of 1.4853.
[0109] A.4) Hydrogenation of the Ester
[0110] A meso/macroporous aluminum oxide support in the form of 4
mm extrudates, possessing a BET surface area of 238 m.sup.2/g and a
pore volume of 0.45 ml/g, was impregnated with an aqueous
ruthenium(III)nitrate solution having a concentration of 0.8% by
weight. 0.15 ml/g (approximately 33% of the total volume) of the
pores of the support possessed a diameter in the range from 50 nm
to 10,000 nm, and 0.30 ml/g (approximately 67% of the total pore
volume) of the pores of the support had a pore diameter in the
range from 2 to 50 nm. The solution volume taken up by the support
in the course of the impregnation corresponded approximately to the
pore volume of the support used. The support impregnated with the
ruthenium(III) nitrate solution was subsequently dried at
120.degree. C. and activated (reduced) in a stream of water at
200.degree. C. The catalyst thus produced contained 0.5% by weight
of ruthenium, based on the weight of the catalyst. A continuously
operated plant consisting of two tubular reactors connected in
series (main reactor 160 ml, d.sub.internal=12 mm, l=1400 mm, and
postreactor 100 ml, d.sub.internal=12 mm, l=1000 mm) was charged
with the catalyst described in the preparation example (main
reactor 71.5 g, postreactor 45.2 g). The main reactor was operated
with circulation in trickle mode (liquid hourly space velocity 12
m/h), the postreactor in straight pass in liquid phase mode. The
phthalic ester prepared in process step 3 was pumped through the
reactor cascade (feed 66 g/h) with pure hydrogen at an average
temperature of 128.degree. C. in the main reactor and 128.degree.
C. in the postreactor, and with a pressure of 200 bar. The catalyst
hourly space velocity in the main reactor was 0.6 kg phthalic
ester/l.sub.cat.times.h. Analysis of the reaction discharge by gas
chromatography showed that >99.9% of the phthalic ester had been
converted.
[0111] The resultant polyester possesses a density of 0.936
g/cm.sup.3, a viscosity of 47 mPa*s at 20.degree. C. determined
according to DIN 51562-1 and a refractive index n.sub.D.sup.20 of
1.462.
[0112] B) Cloud Point Measurement
[0113] The cloud point of the ester according to example A.4 was
determined to be -80.degree. C. according to DIN ISO 3015.
[0114] C) Testing of Compatibility with Sealing Material
[0115] The seal compatibility test with sealing material
acrylonitrile-butadiene-copolymer was performed at 100.degree. C.
for 168 hours according to the standard method ISO 1817 in the
presence of the ester as obtained under A.4).
[0116] The sealing material showed a volume change of +33.3%
(expansion).
[0117] D)
TABLE-US-00004 TABLE 1 Lubricant formulations A and B (all values
in weight-%) Formulation A with Formulation B with Ester DIDA
according to Example A.4 PAO 6 (Nexbase .RTM. 2006, polyalpha-
52.0% 52.0% olefin, obtainable from Neste Oil N.V, Belgium) DIDA
10.0% -- Ester according to Example A.4 -- 10.0% Thickener
(Lubrizol .RTM. 8406, poly- 13.0% 13.0% isobutylene, available from
Lubrizol) Thickener (Lubrizol .RTM. 8407 from 13.0% 13.0% Lubrizol)
Additives (Anglamol .RTM. 6004, additive 12.0% 12.0% package
available from Lubrizol) Viscosity at 40.degree. C. 113.8
mm.sup.2/s 123.3 mm.sup.2/s DIN 51562-1 Viscosity at 100.degree. C.
16.7 mm.sup.2/s 17.0 mm.sup.2/s DIN 51562-1 Viscosity index (VI)
160 150 ASTM D 2270 Density at 15.degree. C. 0.8660 g/ml 0.8686
g/ml DIN 51757 Cloud Point -32.0.degree. C. <-80.0.degree. C.
DIN ISO 3015
[0118] DIDA is commercially available for example as Synative.RTM.
ES DIDA from BASF SE, Ludwigshafen
[0119] The seal compatibility test with sealing material
acrylonitrile-butadiene-copolymer was performed at 100.degree. C.
for 168 hours according to the standard method ISO 1817 in the
presence of formulation A and formulation B, respectively.
[0120] The sealing material showed a volume change of +12.0%
(expansion) in the presence of formulation A and a volume change of
12.6% (expansion) in the presence of formulation B.
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