U.S. patent application number 13/101941 was filed with the patent office on 2012-05-31 for lubricating oil composition.
This patent application is currently assigned to Mitsui Chemicals, Inc.. Invention is credited to Shota ABE, Yuriko Ilmura, Ryousuke Kaneshige, Yasushi Tohi, Michio Toriumi, Junichi Yoshizono.
Application Number | 20120135903 13/101941 |
Document ID | / |
Family ID | 44914400 |
Filed Date | 2012-05-31 |
United States Patent
Application |
20120135903 |
Kind Code |
A1 |
ABE; Shota ; et al. |
May 31, 2012 |
LUBRICATING OIL COMPOSITION
Abstract
A lubricating oil composition comprising: boron atoms from about
5-75 ppm; and 100% by mass being (i) 90 to 10% of a (co)polymer of
specified kinematic viscosity and acid values, primarily derived
from 1-decene, (ii) 5 to 85% of a (co)polymer having specified
kinematic viscosity and molecular weight distribution, mostly
derived from 1-octene, and (iii) 5 to 15% of a fatty acid
ester.
Inventors: |
ABE; Shota; (Ichihara-shi,
JP) ; Kaneshige; Ryousuke; (Kisarazu-shi, JP)
; Ilmura; Yuriko; (Sodegaura-shi, JP) ; Tohi;
Yasushi; (Otake-shi, JP) ; Toriumi; Michio;
(Ichihara-shi, JP) ; Yoshizono; Junichi;
(Iwakuni-shi, JP) |
Assignee: |
Mitsui Chemicals, Inc.
|
Family ID: |
44914400 |
Appl. No.: |
13/101941 |
Filed: |
May 5, 2011 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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61373218 |
Aug 12, 2010 |
|
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Current U.S.
Class: |
508/534 |
Current CPC
Class: |
C10M 2207/282 20130101;
C10N 2030/02 20130101; C10M 169/044 20130101; C10N 2030/04
20130101; C10N 2020/04 20130101; C10N 2030/08 20130101; C10M
2207/281 20130101; C10N 2030/40 20200501; C10M 169/04 20130101;
C10M 2205/028 20130101; C10N 2030/68 20200501; C10M 2207/2815
20130101; C10N 2020/02 20130101; C10N 2030/12 20130101; C10M 111/04
20130101; C10N 2030/06 20130101; C10M 2205/0285 20130101; C10N
2060/14 20130101; C10M 2207/2825 20130101; C10N 2040/04 20130101;
C10M 2205/0285 20130101; C10M 2205/0285 20130101 |
Class at
Publication: |
508/534 |
International
Class: |
C10M 129/68 20060101
C10M129/68 |
Foreign Application Data
Date |
Code |
Application Number |
May 11, 2010 |
JP |
2010-109287 |
Claims
1. A lubricating oil composition comprising the following (i) to
(iii), having a kinematic viscosity at 40.degree. C. of not less
than 30 mm.sup.2/s but not more than 750 mm.sup.2/s and containing
boron atoms in an amount of not less than 5 ppm but not more than
75 ppm, (i) 90 to 10% by mass of a (co)polymer having a kinematic
viscosity at 100.degree. C. of not more than 45 mm.sup.2/s and
having an acid value of less than 0.1 mgKOH/g, not less than 60% by
mol of its constituent units being derived from 1-decene, (ii) 5 to
85% by mass of a (co)polymer having a kinematic viscosity at
100.degree. C. of not less than 35 mm.sup.2/s but not more than
1,500 mm.sup.2/s and having a molecular weight distribution, as
measured by gel permeation chromatography, of not more than 1.8,
not less than 90% by mol of its constituent units being derived
from 1-octene, and (iii) 5 to 15% by mass of a fatty acid ester
having a kinematic viscosity at 100.degree. C. of not more than 20
mm.sup.2/s, with the proviso that the total amount of (i) to (iii)
is 100% by mass.
2. The lubricating oil composition as claimed in claim 1, which
further comprises one or more kinds of extreme pressure agents.
3. The lubricating oil composition as claimed in claim 1, wherein
the kinematic viscosity of the lubricating oil composition at
40.degree. C. is not less than 190 mm.sup.2/s but not more than 750
mm.sup.2/s.
4. The lubricating oil composition as claimed in claim 1, wherein
the kinematic viscosity of the lubricating oil composition at
40.degree. C. is not less than 288 mm.sup.2/s but not more than 352
mm.sup.2/s, and a kinematic viscosity decrease ratio of the
lubricating oil composition at 40.degree. C. after a KRL shear
stability test, as measured in accordance with DIN 52350-6, is less
than 10%.
5. The lubricating oil composition as claimed in claim 1, wherein
the kinematic viscosity of the (co)polymer (ii) at 100.degree. C.
is not less than 150 mm.sup.2/s but not more than 1,200
mm.sup.2/s.
6. The lubricating oil composition as claimed in claim 1, wherein
the kinematic viscosity of the (co)polymer (i) comprising 1-decene
at 100.degree. C. is not more than 11 mm.sup.2/s.
7. A gear for a wind power generator, which is filled with the
lubricating oil composition as claimed in claim 1.
Description
TECHNICAL FIELD
[0001] The present invention relates to a lubricating oil
composition and a gear for a wind power generator, which is filled
with the lubricating oil composition.
BACKGROUND ART
[0002] For grease lubricating oils, gear oils, hydraulic oils,
etc., various properties are required, and in recent years, as the
internal combustion engines and industrial machines are made to
have higher performance and higher output power or as the operation
conditions become severer, higher properties of engine parts, such
as higher abrasion resistance, heat resistance, sludge resistance,
lubricating oil consumption properties and fuel saving, have been
required. The environment where the lubricating oils are used is
becoming severer, while life lengthening of lubricating oils tends
to be required in consideration of environmental problems, and on
that account, decrease in lowering of viscosity attributable to
shear stress given by a gear during the operation of engine, that
is, improvement in shear stability of lubricating oils has been
desired. On the other hand, in order to improve energy conversion
efficiency of engine or ensure favorable lubricating properties of
engine in an extremely low temperature environment, temperature
viscosity properties such that oil films of lubricating oils are
maintained at high temperatures and fluidity of lubricating oils is
rather maintained at low temperatures are regarded as
important.
[0003] Accordingly, as grease lubricating oils, gear oils,
hydraulic oils, etc., those having long life, namely,
low-evaporation properties, and having favorable temperature
viscosity properties are desired.
[0004] Particularly in wind power generators which have been paid
attention as generators of renewable energy in recent years, gear
boxes to convert wind force into electric power are installed at
elevated spots in order to receive more stable wind force. In
addition, from the viewpoint of stable supply of wind force and
direction of wind, they are often installed not only in the inland
areas but also on the sea. On this account, maintenance of gears,
that is, exchange of lubricating oils is very difficult, and as a
result, higher shear stability is required for the lubricating
oils. Moreover, from the viewpoint of efficiency of energy
conversion from wind force into electric power, favorable
lubricating properties at extremely low temperatures such as
-40.degree. C., that is, high fluidity of lubricating oils in a low
temperature environment is desired.
[0005] Furthermore, high anti-micropitting performance is desired
for gear oils for wind power generators. Micropitting is a fatigue
process of gear brought about immediately before gear damage
because of a cycle of excess stress in the rolling
elasto-hydrodynamic lubrication (EHL) region under high load.
Separation of small fragments from gear tooth surface due to
repeated compression stress in this high-load state is referred to
as "micropitting", and for lubricating oils used for gear oils for
wind power generators, high anti-micropitting performance is
desired.
[0006] In view of the above background, developments of various
synthetic lubricating oils have been made (patent literatures 1 and
2, etc.).
PRIOR ART LITERATURE
Patent Literature
[0007] Patent literature 1: National Publication of International
Patent No. 542524/2008 [0008] Patent literature 2: National
Publication of International Patent No. 500489/2009
SUMMARY OF THE INVENTION
Problem to be Solved by the Invention
[0009] However, particularly in the fields where high shear
stability is desired, such as a field of gear oils for wind power
generators, there is room for improvement in the lubricating oil
compositions described in the patent literature 1 and the patent
literature 2.
[0010] The problem to be solved by the present invention relates to
a lubricating oil composition and lubricating oil each of which has
high oxidation stability and heat resistance and is excellent in
temperature viscosity properties, and it is an object of the
present invention to provide a lubricating oil composition having
particularly high shear stability and excellent low-temperature
viscosity properties that are compatible with each other and
further having excellent anti-micropitting performance.
Means to Solve the Problem
[0011] In order to solve the above problem, earnest studies have
been made, and as a result, it has been found that by blending
specific lubricating base oil, a low-molecular weight polymer
having a specific molecular weight distribution which is obtained
by homopolymerizing an .alpha.-olefin of a specific number of
carbon atoms or copolymerizing it with another .alpha.-olefin, and
a specific ester in a specific blending ratio and introducing boron
atoms in a specific amount, the resulting lubricating oil
composition exhibits extremely excellent shear stability,
temperature viscosity properties, low-temperature viscosity
properties and anti-micropitting performance, and the present
invention has been accomplished.
[0012] That is to say, the lubricating oil composition of the
present invention is a lubricating oil composition comprising the
following (i) to (iii), having a kinematic viscosity at 40.degree.
C. of not less than 30 mm.sup.2/s but not more than 750 mm.sup.2/s
and containing boron atoms in an amount of not less than 5 ppm but
not more than 75 ppm,
[0013] (i) 90 to 10% by mass of a (co)polymer having a kinematic
viscosity at 100.degree. C. of not more than 45 mm.sup.2/s and
having an acid value of less than 0.1 mgKOH/g, not less than 60% by
mol of its constituent units being derived from 1-decene,
[0014] (ii) 5 to 85% by mass of a (co)polymer having a kinematic
viscosity at 100.degree. C. of not less than 35 mm.sup.2/s but not
more than 1,500 mm.sup.2/s and having a molecular weight
distribution, as measured by gel permeation chromatography, of not
more than 1.8, not less than 90% by mol of its constituent units
being derived from 1-octene, and
[0015] (iii) 5 to 15% by mass of a fatty acid ester having a
kinematic viscosity at 100.degree. C. of not more than 20
mm.sup.2/s,
[0016] with the proviso that the total amount of (i) to (iii) is
100% by mass.
Effects of the Invention
[0017] By the present invention, a lubricating oil composition
having excellent shear stability as compared with conventional
lubricating oils and further having high temperature viscosity
properties, excellent low-temperature viscosity properties and
anti-micropitting performance is obtained. In particular, a
lubricating oil composition capable of maintaining the above
properties even under high-load conditions which are also referred
to as "extreme pressure lubricating conditions" is obtained.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] FIG. 1 is a view to explain an example of a wind power
generating apparatus of the present invention, and is a partially
cutaway sectional view of the wind power generating apparatus in
the longitudinal direction, and is a perspective view of the wind
power generating apparatus partially visually observed from the
front side of the apparatus.
[0019] FIG. 2 is an enlarged perspective view of X portion of the
wind power generating apparatus shown in FIG. 1, said X portion
being visually observed.
[0020] FIG. 3 is an enlarged perspective view of Y portion of the
wind power generating apparatus shown in FIG. 1, said Y portion
being visually observed.
[0021] FIG. 4 is a diagrammatical perspective view of a driving
strung module used for driving a wind power generating
apparatus.
MODE FOR CARRYING OUT THE INVENTION
Lubricating Oil Composition
[0022] The lubricating oil composition of the present invention has
a kinematic viscosity at 40.degree. C. of not less than 30
mm.sup.2/s but not more than 750 mm.sup.2/s, and more preferably
has a kinematic viscosity at 40.degree. C. of not less than 190
mm.sup.2/s but not more than 750 mm.sup.2/s. When the kinematic
viscosity is not more than 750 mm.sup.2/s, the lubricating oil
composition is excellent in fuel saving performance and energy
conversion efficiency. When the kinematic viscosity at 40.degree.
C. is not less than 30 mm.sup.2/s, the lubricating oil composition
exhibits good lubricating properties at high temperatures, and when
the kinematic viscosity is not less than 190 mm.sup.2/s, the
lubricating oil composition exhibits good lubricating properties as
gear oil in high-load state. When the kinematic viscosity at
40.degree. C. is in the above range, oil films of the lubricating
oils can be sufficiently maintained at high temperatures, and the
lubricating oil composition exhibits more excellent shear
stability.
[0023] The kinematic viscosity of the lubricating oil composition
at 40.degree. C. can be controlled by properly changing the
kinematic viscosity of the below-described decene (co)polymer (i)
and octene (co)polymer (ii) at 100.degree. C. or the amounts of the
decene (co)polymer (i) and the octene (co)polymer (ii) blended. For
example, the kinematic viscosity of the lubricating oil composition
can be controlled based on the blending ratio of the (co)polymers
that is estimated by the method described in JIS K-2283 Annex
1.
[0024] The lubricating oil composition of the present invention
contains (i) a (co)polymer comprising 1-decene and having a
kinematic viscosity at 100.degree. C. of not more than 45
mm.sup.2/s and (ii) a (co)polymer comprising 1-octene and having a
kinematic viscosity at 100.degree. C. of not less than 35
mm.sup.2/s but not more than 1,500 mm.sup.2/s. In the present
specification, the "(co)polymer" includes both of a homopolymer and
a copolymer.
[0025] The total amount of the (co)polymer comprising 1-decene and
the (co)polymer comprising 1-octene is preferably not less than 80%
by mass in the lubricating oil composition of the present
invention. When the total amount thereof is in this range, the
lubricating oil composition has high oxidation stability and heat
resistance.
[0026] In the present invention, the (co)polymer (i) comprising
1-decene and having a kinematic viscosity at 100.degree. C. of not
more than 45 mm.sup.2/s is industrially known by the common name of
poly-.alpha.-olefin (PAO) and is generally used as base oil for
lubricating oils. Such (co)polymers comprising 1-decene are on the
market with the trademarks of, for example, NEXBASE (available from
NESTE OIL CORPORATION), SPECTRASYN (available from EXXONMOBIL
CHEMICAL COMPANY) and DURASYN (available from INEOS), and they are
readily obtainable. Although this (co)polymer is a homopolymer of
1-decene or a copolymer of 1-decene and 1-octene and/or 1-dodecene,
not less than 60% by mol of its constituent units are formed from
1-decene. If the (co)polymer is a copolymer of 1-decene and
1-octene, low-temperature viscosity properties are sometimes
lowered, and if it is a copolymer of 1-decene and 1-dodecene, shear
stability is sometimes lowered. Therefore, a homopolymer of
1-decene is preferably used.
[0027] The acid value of the (co)polymer (i) comprising 1-decene,
as measured by JIS K2501, is preferably less than 0.1 mgKOH/g, and
is more preferably less than 0.05 mgKOH/g. When the acid value is
in this range, the resulting lubricating oil composition is
excellent in oxidation stability and heat resistance.
[0028] The kinematic viscosity of the (co)polymer (i) comprising
1-decene at 100.degree. C. is not more than 45 mm.sup.2/s, and is
preferably not more than 11 mm.sup.2/s. When the kinematic
viscosity is not more than 11 mm.sup.2/s, the lubricating oil
composition exhibits more excellent low-temperature viscosity
properties.
[0029] The (co)polymer (i) comprising 1-decene may be used singly
or may be used as a mixture of two or more kinds.
[0030] The 1-decene (co)polymer can be prepared by a hitherto
publicly known process. For example, by using a catalyst such as
BF.sub.3 or AlCl.sub.3 and controlling polymerization temperature,
polymerization time, etc., a (co)polymer having a desired molecular
weight can be obtained. Through this control of molecular weight
(that is, high-molecular weight gives high viscosity, and
low-molecular weight gives low viscosity), the kinematic viscosity
at 100.degree. C. can be adjusted. In order to adjust the acid
value to less than 0.1 mgKOH/g, the resulting (co)polymer is
generally subjected to hydrogenation process in a publicly known
way. The processes for preparing the 1-decene (co)polymer are
disclosed in U.S. Pat. No. 3,149,178, No. 3,382,291, No. 3,742,082,
No. 3,780,128, No. 4,172,855, No. 4,956,122, etc.
[0031] The (co)polymer (ii) having a kinematic viscosity at
100.degree. C. of not less than 35 mm.sup.2/s but not more than
1,500 mm.sup.2/s is a (co)polymer obtained by polymerizing a
monomer having 8 carbon atoms, namely, 1-octene, and the content of
the constituent units of the monomer is in the range of 90 to 100%
by mol, preferably 95 to 100% by mol. In other words, this
(co)polymer is a homopolymer of 1-octene or a copolymer of 1-octene
and another monomer. When the content is in this range, the
lubricating oil composition of the present invention has properties
substantially equal to those of a lubricating oil composition
containing a polymer obtained by homopolymerizing 1-octene. By
combining the decene (co)polymer (i) with such an octene
(co)polymer (ii) in the lubricating oil composition, shear
stability and low-temperature viscosity properties of the
lubricating oil composition can be improved, and besides, oxidation
stability, heat resistance and temperature viscosity properties can
be also improved. In order to further improve the shear stability
and the low-temperature viscosity properties of the lubricating oil
composition, it is preferable to use a homopolymer of 1-octene
together with the decene (co)polymer (i).
[0032] The monomer to mainly constitute the (co)polymer (ii) is
1-octene. If the monomer is a monomer having 6 carbon atoms,
namely, 1-hexene, temperature viscosity properties and
low-temperature viscosity properties are sometimes markedly
lowered. If the monomer is a monomer having 10 carbon atoms,
namely, 1-decene, shear stability of the lubricating oil
composition is sometimes markedly lowered.
[0033] The shear stability is evaluated by a KRL shear stability
test based on the method described in Deutsche Industrie Normen DIN
52350-6. The lubricating oil composition is allowed to stand at
60.degree. C. for 20 hours under the shearing conditions (1450
rpm), and a kinematic viscosity decrease ratio, that is a ratio of
a kinematic viscosity at 40.degree. C. after the test to a
kinematic viscosity at 40.degree. C. before the test, is evaluated.
As this value is decreased, the rubricating oil composition has
more excellent shear stability.
[0034] 1-Octene that is a raw material can be obtained
inexpensively as compared with 1-decene. In the lubricating oil
composition of the present invention, therefore, the amount of
1-decene used is decreased relatively to the amount of 1-decene in
such a synthetic lubricating oil composition obtained by the prior
art technique as described in the patent literature 1 or the patent
literature 2, so that the lubricating oil composition of the
present invention has an advantage that industrial production at a
low cost becomes feasible.
[0035] Constituent units other than the constituent units of
1-octene to constitute the (co)polymer (ii) are preferably those of
an .alpha.-olefin (except 1-octene) of 2 to 14 carbon atoms, and
the content of such constituent units is in the range of 0 to 10%
by mol, preferably 0 to 5% by mol. When .alpha.-olefins are
selected from the above range, and/or the .alpha.-olefin content is
in the above range, oxidation stability, heat resistance and
low-temperature viscosity properties of the lubricating oil
composition are excellent.
[0036] The kinematic viscosity of the (co)polymer comprising
1-octene at 100.degree. C. in the present invention is not less
than 35 mm.sup.2/s but not more than 1,500 mm.sup.2/s, preferably
not less than 150 mm.sup.2/s but not more than 1,200 mm.sup.2/s.
When the kinematic viscosity is not less than 150 mm.sup.2/s, the
content of the (co)polymer comprising 1-octene, which has a high
viscosity, is decreased relatively to the content of the
(co)polymer comprising 1-decene, which is lubricating base oil in
gear oil, industrial lubricating oil, gear oil for a wind power
generator or lubricating oil for bearing, and therefore, the
lubricating oil composition exhibits excellent low-temperature
viscosity properties. When the kinematic viscosity is not more than
1,200 mm.sup.2/s, the lubricating oil composition exhibits more
excellent shear stability.
[0037] A number-average molecular weight can be measured by gel
permeation chromatography (GPC) calibrated by the use of a standard
substance (monodisperse polystyrene (PSt)) whose molecular weight
is already known, and the number-average molecular weight (Mn) of
the (co)polymer using 1-octene as a monomer in the present
invention is in the range of preferably 500 to 15,000, more
preferably 3,000 to 12,000. When the number-average molecular
weight is in this range, the resulting lubricating oil composition
is excellent in a balance between low-temperature viscosity
properties and shear stability.
[0038] The molecular weight distribution (Mw/Mn) of the (co)polymer
comprising 1-octene in the present invention is in the range of
1.8, preferably in the range of 1.1 to 1.8, more preferably in the
range of 1.2 to 1.7. When the molecular weight distribution is in
this range, shear stability of the resulting lubricating oil
composition is excellent.
[0039] The (co)polymer (ii) comprising octene may be used singly or
may be used as a mixture of two or more kinds.
Preparation of (Co)Polymer (Ii) Comprising Octene in the Present
Invention
[0040] Such a (co)polymer comprising 1-octene as above can be
prepared referring to such catalysts used in the preparation of
.alpha.-olefin (co)polymers as described in Japanese Patent
Laid-Open Publication No. 41303/1990, Japanese Patent Laid-Open
Publication No. 41305/1990, Japanese Patent Laid-Open Publication
No. 274703/1990, Japanese Patent Laid-Open Publication No.
274704/1990, Japanese Patent Laid-Open Publication No. 179005/1991,
Japanese Patent Laid-Open Publication No. 179006/1991, Japanese
Patent Laid-Open Publication No. 193796/1991, Japanese Patent
Laid-Open Publication No. 69394/1992, Japanese Patent Laid-Open
Publication No. 17589/1993, Japanese Patent Laid-Open Publication
No. 122718/1994, Japanese Patent Laid-Open Publication No.
120127/1996, Japanese Patent Laid-Open Publication No. 239414/1996,
Japanese Patent Laid-Open Publication No. 087716/1998, Japanese
Patent Laid-Open Publication No. 212194/2000, WO 01/27124, WO
02/074855, WO 04/029062, EP 0881236 and EP 1416000.
[0041] More specifically, in the preparation of the (co)polymer
using 1-octene as a monomer, a homopolymer or a copolymer can be
obtained by homopolymerizing 1-octene or copolymerizing 1-octene
and the above-mentioned another .alpha.-olefin in the presence of,
for example, an olefin polymerization catalyst comprising:
[0042] (A) a transition metal compound (transition metal compound
of a Group 4 transition metal of the periodic table, or the like),
and
[0043] (B) at least one compound selected from:
[0044] (B-1) an organometallic compound,
[0045] (B-2) an organoaluminum compound,
[0046] (B-3) an organoaluminum oxy-compound, and
[0047] (B-4) a compound which reacts with the Group 4 transition
metal compound (A) to form an ion pair.
[0048] The transition metal compound (A) and the compound (B) are
described below in more detail.
(A) Transition Metal Compound
[0049] As the transition metal compound (A) for use in the present
invention, publicly known periodic table Group IV to Group VI
transition metal compounds having olefin polymerizability are
employable without any restriction. For example, halogenation
products of transition metals of Group IV to Group VI of the
periodic table, alkylation products thereof, alkoxylation products
thereof, and non-bridged or bridged metallocene compounds are
employable. Of these, preferable are halogenation products of
periodic table Group IV transition metals (more preferable are
halogenations products of Group IVB transition metals), alkylation
products thereof, alkoxylation products thereof, and non-bridged or
bridged metallocene compounds. Preferred embodiments of the
transition metal compound (A) are described below.
[0050] Examples of the transition metal halogenation products, the
transition metal alkylation products and the transition metal
alkoxylation products include titanium tetrachloride,
dimethyltitanium dichloride, tetrabenzyltitanium,
tetrabenzylzirconium and tetrabutoxytitanium.
[0051] The non-bridged or bridged metallocene compound is, for
example, a compound represented by the following formula (1) which
is a periodic table Group 4 transition metal compound having
cyclopentadienyl skeleton.
ML.sub.x (1)
[0052] In the above formula, M is a transition metal atom selected
from Group IV of the periodic table, preferably zirconium, titanium
or hafnium of a Group IVB transition metal. x is a valence of the
transition metal and is a number of L. L is a ligand or a group
coordinated to the transition metal; at least one L is a ligand
having cyclopentadienyl skeleton; and L other than the ligand
having cyclopentadienyl skeleton is a group or an atom selected
from a halogen, a hydrogen atom, a hydrocarbon group of 1 to 10
carbon atoms, a neutral, conjugated or non-conjugated diene of 10
or less carbon atoms, an anionic ligand and a neutral ligand
capable of coordination with a lone pair, two or more of said L
being the same or different.
[0053] Examples of the ligands having cyclopentadienyl skeleton
include a cyclopentadienyl group, an alkyl substituted
cyclopentadienyl group, an indenyl group, an alkyl substituted
indenyl group, a 4,5,6,7-tetrahydroindenyl group, a fluorenyl group
and an alkyl substituted fluorenyl group. These groups may be
substituted with halogen atoms, trialkylsilyl groups or the
like.
[0054] When the compound represented by the formula (1) contains
two or more ligands having cyclopentadienyl skeleton, two ligands
having cyclopentadienyl skeleton among them may be bonded to each
other through an alkylene group, a substituted alkylene group, a
silylene group, a substituted silylene group or the like. (Such a
compound is sometimes referred to as a "bridged metallocene
compound" hereinafter, and a compound other than such a compound is
sometimes referred to as a "non-bridged metallocene compound"
hereinafter.)
[0055] Of the above compounds, preferable is, for example, a
compound represented by the following formula (2).
ML.sub.aX.sub.b (2)
[0056] In the above formula, M is a transition metal atom selected
from Group IV of the periodic table, preferably zirconium, titanium
or hafnium of a Group IVB transition metal, L is a ligand
coordinated to the transition metal, a is an integer of 1 or
greater and is a number of L, X is a group or an atom bonded to the
transition metal and selected from a halogen, a hydrogen atom, a
hydrocarbon group of 1 to 10 carbon atoms, a neutral, conjugated or
non-conjugated diene of 10 or less carbon atoms, an anionic ligand
and a neutral ligand capable of coordination with a lone pair, each
X being the same or different, and b is an integer of 1 or greater
and is a number of X.
[0057] In the formula (2), L is a ligand coordinated to the
transition metal, and at least one L is a ligand having
cyclopentadienyl skeleton. Examples of the ligands having
cyclopentadienyl skeleton include a cyclopentadienyl group; alkyl
substituted cyclopentadienyl groups, such as methylcyclopentadienyl
group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl
group, tetramethylcyclopentadienyl group,
pentamethylcyclopentadienyl group, ethylcyclopentadienyl group,
methylethylcyclopentadienyl group, propylcyclopentadienyl group,
methylpropylcyclopentadienyl group, butylcyclopentadienyl group,
methylbutylcyclopentadienyl group and hexylcyclopentadienyl group;
an indenyl group; a 4,5,6,7-tetrahydroindenyl group; and a
fluorenyl group. These groups may be substituted with halogen
atoms, trialkylsilyl groups or the like.
[0058] In the formula (2), a is an integer of 1 or greater and is a
number of L.
[0059] In the formula (2), M is zirconium, titanium or hafnium.
[0060] X is a group or an atom bonded to the transition metal and
selected from a halogen, a hydrogen atom, a hydrocarbon group of 1
to 10 carbon atoms, a neutral, conjugated or non-conjugated diene
of 10 or less carbon atoms, an anionic ligand and a neutral ligand
capable of coordination with a lone pair, and each X is the same or
different. Examples of the halogens are fluorine, chlorine, bromine
and iodine. Examples of the hydrocarbon groups include methyl,
ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl,
2,2-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl,
1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl,
1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl,
cyclohexylmethyl, cyclohexyl and 1-methyl-1-cyclohexyl. Examples of
the neutral, conjugated or non-conjugated dienes of 10 or less
carbon atoms include s-cis- or s-trans-.eta..sup.4-1,3-butadiene,
s-cis- or s-trans-.eta..sup.4-1,4-diphenyl-1,3-butadiene, s-cis- or
s-trans-.eta..sup.4-3-methyl-1,3-pentadiene, s-cis- or
s-trans-.eta..sup.4-1,4-dibenzyl-1,3-butadiene, s-cis- or
s-trans-.eta..sup.4-2,4-hexadiene, s-cis- or
s-trans-.eta..sup.4-1,3-pentadiene, s-cis- or
s-trans-.eta..sup.4-1,4-ditolyl-1,3-butadiene, and s-cis- or
s-trans-.eta..sup.4-1,4-bis(trimethylsilyl)-1,3-butadiene. Examples
of the anionic ligands include alkoxy groups, such as methoxy,
tert-butoxy and phenoxy; carboxylate groups, such as acetate and
benzoate; and sulfonate groups, such as mesylate and tosylate.
Examples of the neutral ligands capable of coordination with a lone
pair include organic phosphorus compounds, such as
trimethylphosphine, triethylphosphine, triphenylphosphine and
diphenylmethylphosphine; and ethers, such as tetrahydrofuran,
diethyl ether, dioxane and 1,2-dimethoxyethane. Each X may be the
same or different.
[0061] In the formula (2), b is an integer of 1 or greater and is a
number of X.
[0062] When the compound represented by the formula (2) contains
two or more ligands having cyclopentadienyl skeleton, two ligands
having cyclopentadienyl skeleton among them may be bonded to each
other through an alkylene group, such as ethylene or propylene; a
substituted alkylene group, such as diphenylmethylene; an
alkylidene group, such as isopropylidene; a silylene group; or a
substituted silylene group, such as dimethylsilylene group,
diphenylsilylene group or methylphenylsilylene group. Two or more
ligands having cyclopentadienyl skeleton may be the same or
different.
[0063] When the compound represented by the formula (2) contains
two ligands having cyclopentadienyl group, this compound is more
specifically represented by the following formula (3) or (4).
##STR00001##
[0064] In the above formula, M is a transition metal atom selected
from Group IV of the periodic table, preferably zirconium, titanium
or hafnium of a Group IVB transition metal, R.sup.1, R.sup.2,
R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9 and
R.sup.10 are each selected from hydrogen, a hydrocarbon group and a
silicon-containing hydrocarbon group and may be the same or
different, neighboring substituents among R.sup.1 to R.sup.10 may
be bonded to each other to form a ring, X is a group or an atom
selected from a halogen, a hydrogen atom, a hydrocarbon group of 1
to 10 carbon atoms, a neutral, conjugated or non-conjugated diene
of 10 or less carbon atoms, an anionic ligand and a neutral ligand
capable of coordination with a lone pair, each X being the same or
different, and n is 1 or 2 and is a number of X.
##STR00002##
[0065] In the above formula, M is a transition metal atom selected
from Group IV of the periodic table, preferably zirconium, titanium
or hafnium of a Group IVB transition metal, R.sup.1, R.sup.2,
R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are each
selected from hydrogen, a hydrocarbon group and a
silicon-containing hydrocarbon group and may be the same or
different, neighboring substituents among R.sup.1 to R.sup.8 may be
bonded to each other to form a ring, X is a group or an atom
selected from a halogen, a hydrogen atom, a hydrocarbon group of 1
to 10 carbon atoms, a neutral, conjugated or non-conjugated diene
of 10 or less carbon atoms, an anionic ligand and a neutral ligand
capable of coordination with a lone pair, each X being the same or
different, n is 1 or 2 and is a number of X, Q is selected from
carbon, silicon and germanium, and Y.sup.1 and Y.sup.2 are each
selected from hydrogen, a hydrocarbon group and a
silicon-containing group, may be the same or different and may be
bonded to each other to form a ring.
[0066] In the formulas (3) and (4), the hydrocarbon group is
preferably an alkyl group of 1 to 20 carbon atoms, an arylalkyl
group of 7 to 20 carbon atoms, an aryl group of 6 to 20 carbon
atoms or an alkylaryl group of 7 to 20 carbon atoms, and may
contain one or more ring structures. Examples of such groups
include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl,
1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,1-diethylpropyl,
1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl,
tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl,
cyclohexylmethyl, cyclohexyl, 1-methyl-1-cyclohexyl, 1-adamantyl,
2-adamantyl, 2-methyl-2-adamantyl, menthyl, norbornyl, benzyl,
2-phenylethyl, 1-tetrahydronaphthyl, 1-methyl-1-tetrahydronaphthyl,
phenyl, naphthyl and tolyl.
[0067] In the formulas (3) and (4), the silicon-containing
hydrocarbon group is preferably an alkylsilyl or arylsilyl group
having 1 to 4 silicon atoms and 3 to 20 carbon atoms. Examples of
such groups include trimethylsilyl, tert-butyldimethylsilyl and
triphenylsilyl.
[0068] In the present invention, R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9 and R.sup.10
in the formula (3) are each selected from hydrogen, a hydrocarbon
group and a silicon-containing hydrocarbon group, and they may be
the same or different. Preferred examples of the hydrocarbon groups
and the silicon-containing hydrocarbon groups include those
previously described. R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5,
R.sup.6, R.sup.7 and R.sup.8 in the formula (4) are each selected
from hydrogen, a hydrocarbon group and a silicon-containing
hydrocarbon group, and they may be the same or different. Preferred
examples of the hydrocarbon groups and the silicon-containing
hydrocarbon groups include those previously described.
[0069] Neighboring substituents among R.sup.1 to R.sup.10 on the
cyclopentadienyl rings in the formula (3) may be bonded to each
other to form a ring. Examples of such substituted cyclopentadienyl
groups include indenyl, 2-methylindenyl, tetrahydroindenyl,
2-methyltetrahydroindenyl, 2,4,4-trimethyltetrahydroindenyl,
fluorenyl, benzofluorenyl, dibenzofluorenyl,
octahydrodibenzofluorenyl and octamethyloctahydrodibenzofluorenyl.
Neighboring substituents among R.sup.1 to R.sup.8 on the
cyclopentadienyl rings in the formula (4) may be bonded to each
other to form a ring. Examples of such substituted cyclopentadienyl
groups include indenyl, 2-methylindenyl, tetrahydroindenyl,
2-methyltetrahydroindenyl, 2,4,4-trimethyltetrahydroindenyl,
fluorenyl, benzofluorenyl, dibenzofluorenyl,
octahydrodibenzofluorenyl and
octamethyloctahydrodibenzofluorenyl.
[0070] In the present invention, M in the formulas (3) and (4) is a
transition metal atom selected from Group IV of the periodic table,
preferably zirconium, titanium or hafnium of a Group IVB transition
metal.
[0071] X is a group or an atom selected from a halogen, a hydrogen
atom, a hydrocarbon group of 1 to 10 carbon atoms, a neutral,
conjugated or non-conjugated diene of 10 or less carbon atoms, an
anionic ligand and a neutral ligand capable of coordination with a
lone pair, and each X is the same or different. Examples of the
halogens are fluorine, chlorine, bromine and iodine. Examples of
the hydrocarbon groups include methyl, ethyl, n-propyl, isopropyl,
2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl,
1,1-diethylpropyl, 1-ethyl-1-methylpropyl,
1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl,
1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl,
cyclohexylmethyl, cyclohexyl and 1-methyl-1-cyclohexyl. Examples of
the neutral, conjugated or non-conjugated dienes of 10 or less
carbon atoms include s-cis- or s-trans-.eta..sup.4-1,3-butadiene,
s-cis- or s-trans-.eta..sup.4-1,4-diphenyl-1,3-butadiene, s-cis- or
s-trans-.eta..sup.4-3-methyl-1,3-pentadiene, s-cis- or
s-trans-.eta..sup.4-1,4-dibenzyl-1,3-butadiene, s-cis- or
s-trans-.eta..sup.4-2,4-hexadiene, s-cis- or
s-trans-.eta..sup.4-1,3-pentadiene, s-cis- or
s-trans-.eta..sup.4-1,4-ditolyl-1,3-butadiene, and s-cis- or
s-trans-.eta..sup.4-1,4-bis(trimethylsilyl)-1,3-butadiene. Examples
of the anionic ligands include alkoxy groups, such as methoxy,
tert-butoxy and phenoxy; carboxylate groups, such as acetate and
benzoate; and sulfonate groups, such as mesylate and tosylate.
Examples of the neutral ligands capable of coordination with a lone
pair include organic phosphorus compounds, such as
trimethylphosphine, triethylphosphine, triphenylphosphine and
diphenylmethylphosphine; and ethers, such as tetrahydrofuran,
diethyl ether, dioxane and 1,2-dimethoxyethane. Each X may be the
same or different.
[0072] n is 1 or 2 and is a number of X.
[0073] Examples of the compounds represented by the formula (3)
include cyclopentadienyl trichloride, cyclopentadienylzirconium
trichloride, bis(cyclopentadienyl)titanium dichloride,
bis(cyclopentadienyl)zirconium dichloride,
bis(pentamethylcyclopentadienyl)zirconium dichloride,
(cyclopentadienyl)(pentamethylcyclopentadienyl)zirconium
dichloride, bis(methylcyclopentadienyl)zirconium dichloride,
bis(ethylcyclopentadienyl)zirconium dichloride,
bis(propylcyclopentadienyl)zirconium dichloride,
bis(butylcyclopentadienyl)zirconium dichloride such as
bis(n-butylcyclopentadienyl)zirconium dichloride,
bis(dimethlcyclopentadienyl)zirconium dichloride such as
bis(1,3-dimethlcyclopentadienyl)zirconium dichloride,
bis(diethylcyclopentadienyl)zirconium dichloride such as
bis(1,3-diethylcyclopentadienyl)zirconium dichloride,
bis(methylethylcyclopentadienyl)zirconium dichloride,
bis(methylpropylcyclopentadienyl)zirconium dichloride such as
bis(1-methyl-3-n-propylcyclopentadienyl)zirconium dichloride, and
bis(methylbutylcyclopentadienyl)zirconium dichloride such as
bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride.
Examples of the compounds represented by the formula (4) include
[0074] ethylenebis(indenyl)zirconium dichloride, [0075]
ethylenebis(1-indenyl)titanium dichloride, [0076]
ethylenebis(4,5,6,7-tetrahydroindenyl)zirconium dichloride, [0077]
dimethylsilylenebis(methylcyclopentadienyl)zirconium dichloride,
[0078] dimethylsilylenebis(dimethylcyclopentadienyl)zirconium
dichloride, [0079]
dimethylsilylenebis(di-tert-butylcyclopentadienyl)zirconium
dichloride, [0080] dimethylsilylenebis(indenyl)zirconium
dichloride, [0081] dimethylsilylenebis(2-methylindenyl)zirconium
dichloride, [0082]
dimethylsilylenebis(2-methyl-4,5-benzindenyl)zirconium dichloride,
[0083] dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium
dichloride, [0084]
dimethylsilylenebis(2-methyl-4-naphthylindenyl)zirconium
dichloride, [0085] dimethylethylenebis(2-methylindenyl)zirconium
dichloride, [0086]
dimethylethylenebis(2-methyl-4,5-benzindenyl)zirconium dichloride,
[0087] dimethylethylenebis(2-methyl-4-phenylindenyl)zirconium
dichloride, [0088]
dimethylethylenebis(2-methyl-4-naphthylindenyl)zirconium
dichloride, [0089]
isopropylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride,
[0090]
isopropylidene(cyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium
dichloride, [0091]
isopropylidene(methylcyclopentadienyl)(fluorenyl)zirconium
dichloride, [0092]
isopropylidene(tert-butylcyclopentadienyl)(fluorenyl)zirconium
dichloride, [0093]
isopropylidene(methyl-tert-butylcyclopentadienyl)(fluorenyl)zirconium
dichloride, [0094]
isopropylidene(methyl-tert-butylcyclopentadienyl)(3,6-di-tert-butylfluore-
nyl)zirconium dichloride, [0095]
isopropylidene(methyl-tert-butylcyclopentadienyl)(octamethyloctahydridodi-
benzofluorenyl)zirconium dichloride, [0096]
diphenylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,
[0097]
diphenylmethylene(cyclopentadienyl)(3,6-di-t-butylfluorenyl)zircon-
ium dichloride, [0098]
diphenylmethylene(methylcyclopentadienyl)(fluorenyl)zirconium
dichloride, [0099]
diphenylmethylene(tert-butylcyclopentadienyl)(fluorenyl)zirconium
dichloride, [0100]
diphenylmethylene(methyl-tert-butylcyclopentadienyl)(fluorenyl)zirconium
dichloride, [0101]
diphenylmethylene(methyl-tert-butylcyclopentadienyl)(3,6-di-tert-butylflu-
orenyl)zirconium dichloride, [0102]
diphenylmethylene(methyl-tert-butylcyclopentadienyl)(octamethyloctahydrid-
odibenzofluorenyl)zirconium dichloride, [0103]
cyclohexylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,
[0104]
cyclohexylene(cyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium
dichloride, [0105]
cyclohexylene(methylcyclopentadienyl)(fluorenyl)zirconium
dichloride, [0106]
cyclohexylene(tert-butylcyclopentadienyl)(fluorenyl)zirconium
dichloride, [0107]
cyclohexylene(methyl-tert-butylcyclopentadienyl)(fluorenyl)zirconium
dichloride, [0108]
cyclohexylene(methyl-tert-butylcyclopentadienyl)(3,6-di-tert-butylfluoren-
yl)zirconium dichloride, [0109]
cyclohexylene(methyl-tert-butylcyclopentadienyl)(octamethyloctahydridodib-
enzofluorenyl)zirconium dichloride, [0110]
di(p-tolyl)methylene(cyclopentadienyl)(fluorenyl)zirconium
dichloride, [0111]
di(p-tolyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)-
zirconium dichloride, [0112]
di(p-tolyl)methylene(cyclopentadienyl)(2,7-dimethylfluorenyl)zirconium
dichloride, [0113]
di(p-tolyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconi-
um dichloride, [0114]
di(p-tert-butylphenyl)methylene(cyclopentadienyl)(fluorenyl)zirconium
dichloride, [0115]
di(p-tert-butylphenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluore-
nyl)zirconium dichloride, [0116]
di(p-tert-butylphenyl)methylene(cyclopentadienyl)(2,7-dimethylfluorenyl)z-
irconium dichloride, [0117]
di(p-tert-butylphenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluore-
nyl)zirconium dichloride, [0118]
di(p-n-butylphenyl)methylene(cyclopentadienyl)(fluorenyl)zirconium
dichloride, [0119]
di(p-n-butylphenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl-
)zirconium dichloride, [0120]
di(p-n-butylphenyl)methylene(cyclopentadienyl)(2,7-dimethylfluorenyl)zirc-
onium dichloride, [0121]
di(p-n-butylphenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl-
)zirconium dichloride, [0122]
di(m-tolyl)methylene(cyclopentadienyl)(fluorenyl)zirconium
dichloride, [0123]
di(m-tolyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)-
zirconium dichloride, [0124]
di(m-tolyl)methylene(cyclopentadienyl)(2,7-dimethylfluorenyl)zirconium
dichloride, [0125]
di(m-tolyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconi-
um dichloride, [0126]
di(p-tolyl)methylene(cyclopentadienyl)(fluorenyl)zirconium
dimethyl, [0127]
di(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzof-
luorenyl)zirconium dichloride, [0128]
di(p-tert-butylphenyl)methylene(cyclopentadienyl)(cyclopentadienyl)(octam-
ethyloctahydrodibenzofluorenyl)zirconium dichloride, [0129]
di(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluoreny-
l)zirconium dimethyl, [0130]
di(p-tert-butylphenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluore-
nyl)zirconium dichloride, [0131]
di(p-tolyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconi-
um dimethyl, [0132]
di(p-isopropylphenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluoren-
yl)zirconium dichloride, [0133]
di(p-tert-butylpheyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluoren-
yl)zirconium dichloride, [0134]
di(4-biphenyl)methylene(cyclopentadienyl)(fluorenyl)zirconium
dichloride, [0135]
di(4-biphenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoren-
yl)zirconium dichloride, [0136]
di(4-biphenyl)methylene(cyclopentadienyl)(2,7-dimethylfluorenyl)zirconium
dichloride, [0137]
di(4-biphenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirc-
onium dichloride, [0138]
cyclopentylidene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconium
dichloride, [0139]
cyclohexylidene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconium
dichloride, [0140]
adamantylidene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconium
dichloride, [0141]
monophenylmonomethylmethylene(cyclopentadienyl)(2,7-di-tert-butylfluoreny-
l)zirconium dichloride, [0142]
dimethylmethylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconium
dichloride, [0143]
diphenylmethylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconium
dichloride, [0144]
di(p-tolyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconi-
um dichloride, [0145]
diethylmethylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconium
dichloride, [0146]
cyclopentylidene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium
dichloride, [0147]
cyclohexylidene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium
dichloride, [0148]
adamantylidene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium
dichloride, [0149]
monophenylmonomethylmethylene(cyclopentadienyl)(3,6-di-tert-butylfluoreny-
l)zirconium dichloride, [0150]
dimethylmethylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium
dichloride, [0151]
diphenylmethylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium
dichloride, [0152]
di(p-tolyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconi-
um dichloride, [0153]
diethylmethylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium
dichloride, [0154]
cyclopentylidene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zi-
rconium dichloride, [0155]
cyclohexylidene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zir-
conium dichloride, [0156]
adamantylidene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirc-
onium dichloride, [0157]
monophenylmonomethylmethylene(cyclopentadienyl)(octamethyloctahydrodibenz-
ofluorenyl)zirconium dichloride, [0158]
dimethylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)z-
irconium dichloride, [0159]
diphenylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)z-
irconium dichloride, [0160]
di(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluoreny-
l)zirconium dichloride, [0161]
diethylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zi-
rconium dichloride, [0162]
cyclopentylidene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluore-
nyl)zirconium dichloride, [0163]
cyclohexylidene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluoren-
yl)zirconium dichloride, [0164]
adamantylidene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluoreny-
l)zirconium dichloride, [0165]
monophenylmonomethylmethylene(cyclopentadienyl)(octamethyltetrahydrodicyc-
lopentafluorenyl)zirconium dichloride, [0166]
dimethylmethylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluor-
enyl)zirconium dichloride, [0167]
diphenylmethylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluor-
enyl)zirconium dichloride, [0168]
di(p-tolyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafl-
uorenyl)zirconium dichloride, [0169]
diethylmethylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluore-
nyl)zirconium dichloride, [0170]
cyclopentylidene(cyclopentadienyl)(dibenzofluorenyl)zirconium
dichloride, [0171]
cyclohexylidene(cyclopentadienyl)(dibenzofluorenyl)zirconium
dichloride, [0172]
adamantylidene(cyclopentadienyl)(dibenzofluorenyl)zirconium
dichloride, [0173]
monophenylmonomethylmethylene(cyclopentadienyl)(dibenzofluorenyl)z-
irconium dichloride, [0174]
dimethylmethylene(cyclopentadienyl)(dibenzofluorenyl)zirconium
dichloride, [0175]
diphenylmethylene(cyclopentadienyl)(dibenzofluorenyl)zirconium
dichloride, [0176]
di(p-tolyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zirconium
dichloride, [0177]
diethylmethylene(cyclopentadienyl)(dibenzofluorenyl)zirconium
dichloride, [0178] ethylene(cyclopentadienyl)(fluorenyl)zirconium
dichloride, [0179]
ethylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconium
dichloride, [0180]
ethylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium
dichloride, [0181]
ethylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)zirc-
onium dichloride, [0182]
ethylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium
dichloride, [0183] propylene(cyclopentadienyl)(fluorenyl)zirconium
dichloride, [0184]
propylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconium
dichloride, [0185] propylene(cyclopentadienyl)
(3,6-di-tert-butylfluorenyl)zirconium dichloride, [0186]
propylene(cyclopentadienyl)(octamethyltetrahydrodicyclopentafluorenyl)zir-
conium dichloride, [0187]
propylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium
dichloride, [0188]
(methyl)(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofl-
uorenyl)zirconium dichloride, [0189]
(methyl)(phenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzoflu-
orenyl)zirconium dichloride, [0190]
(methyl)(p-tolyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)z-
irconium dichloride, [0191] (methyl)(phenyl)methylene
(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconium dichloride,
[0192]
(methyl)(p-tolyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluo-
renyl)zirconium dichloride, [0193] (methyl)(phenyl)methylene
(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride,
[0194]
(methyl)(benzyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluor-
enyl)zirconium dichloride, [0195]
(methyl)(benzyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zi-
rconium dichloride, [0196]
(methyl)(benzyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zi-
rconium dichloride, [0197]
(methyl)(benzyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zi-
rconium dichloride, [0198]
(methyl)(benzyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzoflu-
orenyl)zirconium dichloride, and [0199]
(methyl)(benzyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzoflu-
orenyl)zirconium dichloride.
[0200] Further, not only titanium compounds and hafnium compounds
having similar stereostructure, bromides and iodides but also such
transition metal compounds as described in, for example, Japanese
Patent Laid-Open Publication No. 9913/1991, Japanese Patent
Laid-Open Publication No. 131488/1990, Japanese Patent Laid-Open
Publication No. 21607/1991, Japanese Patent Laid-Open Publication
No. 106907/1991, Japanese Patent Laid-Open Publication No.
188092/1991, Japanese Patent Laid-Open Publication No. 69394/1992,
Japanese Patent Laid-Open Publication No. 300887/1992 and WO
01/27124A1 can be also mentioned.
[0201] The transition metal compound (A) used in the polymerization
examples of the present invention and the comparative
polymerization examples is specifically a compound of the following
formula (6), but in the present invention, the transition metal
compound (A) is not limited to this compound. A transition metal
compound (A) represented by the following formula (5), (7), (8) or
(9) may be used.
##STR00003##
[0202] In the polymerization examples of the present invention, the
compound (6) is described as [0203]
(methyl)(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofl-
uorenyl)zirconium dichloride.
[0204] The structure of the transition metal compound obtained is
determined by 270 MHz .sup.1H-NMR (GSH-270 of JEOL Ltd.) and
FD-mass spectrometry (SX-102A of JEOL Ltd.).
[0205] The above transition metal compounds (A) may be used singly
or may be used in combination of two or more kinds.
(B-1) Organometallic Compound
[0206] As the organometallic compound (B-1), an organometallic
compound represented by the following formula (10) is specifically
used.
[0207] A dialkyl compound of a periodic table Group 2 or Group 12
metal, which is represented by the following formula:
R.sup.aR.sup.bM.sup.3 (10)
[0208] wherein R.sup.a and R.sup.b may be the same as or different
from each other and are each a hydrocarbon group of 1 to 15 carbon
atoms, preferably 1 to 4 carbon atoms, and M.sup.3 is Mg, Zn or
Cd.
[0209] Such organometallic compounds (B-1) may be used singly or in
combination of two or more kinds.
(B-2) Organoaluminum Compound
[0210] The organoaluminum compound (B-2) for forming the olefin
polymerization catalyst is, for example, an organoaluminum compound
represented by the following formula (11), or an alkyl complex
compound of a Group 1 metal and aluminum, which is represented by
the following formula (12).
[0211] An organoaluminum compound represented by the formula
(11):
R.sup.a.sub.mAl(OR.sup.b).sub.nH.sub.pX.sup.2.sub.q (11)
wherein R.sup.a and R.sup.b may be the same as or different from
each other and are each a hydrocarbon group of 1 to 15 carbon
atoms, preferably 1 to 4 carbon atoms, X.sup.2 is a halogen atom,
and m, n, p and q are numbers satisfying the conditions of
0<m.ltoreq.3, 0.ltoreq.n<3, 0.ltoreq.p<3, 0.ltoreq.q<3
and m+n+p+q=3.
[0212] Examples of such compounds include trimethylaluminum,
triethylaluminum, triisobutylaluminum and diisobutylaluminum
hydride.
[0213] An alkyl complex compound of a periodic table Group 1 metal
and aluminum, which is represented by the formula (12):
M.sup.2AlR.sup.a.sub.4 (12)
[0214] wherein M.sup.2 is Li, Na or K, and R.sup.a is a hydrocarbon
group of 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.
[0215] Examples of such compounds include LiAl
(C.sub.2H.sub.5).sub.4 and LiAl (C.sub.7H.sub.15).sub.4.
[0216] The organoaluminum compound represented by the formula (11)
is, for example, a compound represented by the following formula
(13), (14), (15) or (16).
R.sup.a.sub.mAl(OR.sup.b).sub.3-m (13)
wherein R.sup.a and R.sup.b may be the same as or different from
each other and are each a hydrocarbon group of 1 to 15 carbon
atoms, preferably 1 to 4 carbon atoms, and m is preferably a number
of 1.5.ltoreq.m.ltoreq.3.
R.sup.a.sub.mAlX.sup.2.sub.3-m (14)
wherein R.sup.a is a hydrocarbon group of 1 to 15 carbon atoms,
preferably 1 to 4 carbon atoms, X.sup.2 is a halogen atom, and m is
preferably a number of 0<m<3.
R.sup.a.sub.mAlH.sub.3-m (15)
wherein R.sup.a is a hydrocarbon group of 1 to 15 carbon atoms,
preferably 1 to 4 carbon atoms, and m is preferably a number of
2.ltoreq.m<3.
R.sup.a.sub.mAl(OR.sup.b).sub.nX.sup.2.sub.q (16)
wherein R.sup.a and R.sup.b may be the same as or different from
each other and are each a hydrocarbon group of 1 to 15 carbon
atoms, preferably 1 to 4 carbon atoms, X.sup.2 is a halogen atom,
and m, n and q are numbers satisfying the conditions of
0<m.ltoreq.3, 0n.ltoreq.n<3, 0.ltoreq.q<3 and m+n+q=3.
[0217] Examples of the aluminum compounds represented by the
formula (13), (14), (15) or (16) include tri-n-alkylaluminums, such
as trimethylaluminum, triethylaluminum, tri-n-butylaluminum,
tripropylaluminum, tripentylaluminum, trihexylaluminum,
trioctylaluminum and tridecylaluminum; branched chain
trialkylaluminums, such as triisopropylaluminum,
triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum,
tri-2-methylbutylaluminum, tri-3-methylbutylaluminum,
tri-2-methylpentylaluminum, tri-3-methylpentylaluminum,
tri-4-methylpentylaluminum, tri-2-methylhexylaluminum,
tri-3-methylhexylaluminum and tri-2-ethylhexylaluminum;
tricycloalkylaluminums, such as tricyclohexylaluminum and
tricyclooctylaluminum; triarylaluminums, such as triphenylaluminum
and tritolylaluminum; dialkylaluminum hydrides, such as
diisopropylaluminum hydride and diisobutylaluminum hydride;
alkenylaluminums represented by the formula
(i-C.sub.4H.sub.9).sub.xAl.sub.y(C.sub.5H.sub.10).sub.z (x, y and z
are each a positive number, and z.ltoreq.2x), such as
isoprenylaluminum; alkylaluminum alkoxides, such as
isobutylaluminum methoxide, isobutylaluminum ethoxide and
isobutylaluminum isopropoxide; dialkylaluminum alkoxides, such as
dimethylaluminum methoxide, diethylaluminum ethoxide and
dibutylaluminum butoxide; alkylaluminum sesquialkoxides, such as
ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide;
partially alkoxylated alkylaluminums having average composition
represented by the formula R.sup.a.sub.2.5Al(OR.sup.b).sub.0.5;
alkylaluminum aryloxides, such as diethylaluminum phenoxide,
diethylaluminum(2,6-di-t-butyl-4-methylphenoxide),
ethylaluminumbis(2,6-di-t-butyl-4-methylphenoxide),
diisobutylaluminum(2,6-di-t-butyl-4-methylphenoxide) and
isobutylaluminumbis(2,6-di-t-butyl-4-methylphenoxide);
dialkylaluminum halides, such as dimethylaluminum chloride,
diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum
bromide and diisobutylaluminum chloride; alkylaluminum
sesquihalides, such as ethylaluminum sesquichloride, butylaluminum
sesquichloride and ethylaluminum sesequibromide; partially
halogenated alkylaluminums, such as alkylaluminum dihalides,
specifically ethylaluminum dichloride, propylaluminum dichloride
and butylaluminum dibromide; dialkylaluminum hydrides, such as
diethylaluminum hydride and dibutylaluminum hydride; partially
hydrogenated alkylaluminums, such as alkylaluminum dihydrides,
specifically ethylaluminum dihydride and propylaluminum dihydride;
and partially alkoxylated and halogenated alkylaluminums, such as
ethylaluminum ethoxychloride, butylaluminum butoxychloride and
ethylaluminum ethoxybromide.
[0218] Further, compounds analogous to the compound represented by
the formula (11) are also employable, and for example, an
organoaluminum compound wherein two or more aluminum compounds are
bonded through a nitrogen atom is employable. An example of such a
compound is
(C.sub.2H.sub.5).sub.2AlN(C.sub.2H.sub.5)Al(C.sub.2H.sub.5).sub.2.
[0219] Examples of the compounds represented by the formula (12)
include LiAl(C.sub.2H.sub.5).sub.4 and
LiAl(C.sub.7H.sub.15).sub.4.
[0220] Further, compounds by the use of which the above-mentioned
organoaluminum compounds are formed in the polymerization system
are also employable, and for example, a combination of aluminum
halide and alkyllithium or a combination of aluminum halide and
alkylmagnesium is also employable.
[0221] Of the above compounds, organoaluminum compounds are
preferable.
[0222] The organoaluminum compounds represented by the formula (11)
or the alkyl complex compounds of Group 1 metals and aluminum which
are represented by the formula (12) are used singly or in
combination of two or more kinds.
(B-3) Organoaluminum Oxy-Compound
[0223] The organoaluminum oxy-compound (B-3) may be hitherto
publicly known aluminoxane, or may be such a benzene-insoluble
organoaluminum oxy-compound as given as an example in Japanese
Patent Laid-Open Publication No. 78687/1990.
[0224] The hitherto publicly known aluminoxane can be prepared by
following processes, and is usually obtained as a solution of a
hydrocarbon solvent.
[0225] (I) A process comprising adding an organoaluminum compound,
such as trialkylaluminum, to a hydrocarbon medium suspension of a
compound containing adsorbed water or a salt containing water of
crystallization, such as magnesium chloride hydrate, copper sulfate
hydrate, aluminum sulfate hydrate, nickel sulfate hydrate or cerous
chloride hydrate, to allow adsorbed water or water of
crystallization to react with the organoaluminum compound.
[0226] (II) A process comprising allowing water, ice or water vapor
to directly act on an organoaluminum compound, such as
trialkylaluminum, in a medium, such as benzene, toluene, ethyl
ether or tetrahydrofuran.
[0227] (III) A process comprising allowing an organotin oxide, such
as dimethyltin oxide or dibutyltin oxide, to react with an
organoaluminum compound, such as trialkylaluminum, in a medium,
such as decane, benzene or toluene.
[0228] The aluminoxane may contain a small amount of an
organometallic component. After a solvent or an unreacted
organoaluminum compound is removed from the recovered solution of
aluminoxane by distillation, the residue may be redissolved in a
solvent or suspended in a poor solvent for aluminoxane.
[0229] Examples of the organoaluminum compounds used for preparing
aluminoxane include the same organoaluminum compounds as those
given as examples of the aforesaid organoaluminum compounds
(B-2).
[0230] Of those compounds, trialkylaluminums and
tricycloalkylaluminums are preferable, and trimethylaluminum is
particularly preferable.
[0231] Such organoaluminum compounds are used singly or in
combination of two or more kinds.
[0232] The benzene-insoluble organoaluminum oxy-compound is
preferably a compound usually having a content of an Al component
soluble in benzene at 60.degree. C., of not more than 10%,
preferably not more than 5%, particularly preferably not more than
2%, in terms of Al atom, that is, a compound which is insoluble or
slightly soluble in benzene.
[0233] Aluminoxane prepared from trimethylaluminum is called
methylaluminoxane or MAO, and is a compound particularly frequently
used.
[0234] Examples of the solvents used for preparing aluminoxane
include hydrocarbon solvents, e.g., aromatic hydrocarbons, such as
benzene, toluene, xylene, cumene and cymene; aliphatic
hydrocarbons, such as pentane, hexane, heptane, octane, decane,
dodecane, hexadecane and octadecane; alicyclic hydrocarbons, such
as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane;
petroleum fractions, such as gasoline, kerosine and gas oil; and
halogenation products of the above aromatic hydrocarbons, aliphatic
hydrocarbons and alicyclic hydrocarbons, particularly chlorination
products and bromination products thereof. Further, ethers, such as
ethyl ether and tetrahydrofuran, are also employable. Of these
solvents, aromatic hydrocarbons or aliphatic hydrocarbons are
particularly preferable.
[0235] As the organoaluminum oxy-compound, an organoaluminum
oxy-compound containing boron, which is represented by the
following formula (17), can be also mentioned.
##STR00004##
[0236] In the above formula, R.sup.c is a hydrocarbon group of 1 to
10 carbon atoms, and each R.sup.d may be the same or different and
is a hydrogen atom, a halogen atom or a hydrocarbon group of 1 to
10 carbon atoms.
[0237] The organoaluminum oxy-compound containing boron, which is
represented by the formula (17), can be prepared by allowing an
alkylboronic acid represented by the following formula (18) to
react with an organoaluminum compound in an inert solvent at a
temperature of -80.degree. C. to room temperature for a period of 1
minute to 24 hours in an inert gas atmosphere.
R.sup.cB(OH).sub.2 (18)
[0238] In the above formula, R.sup.c is the same group as described
above.
[0239] Examples of the alkylboronic acids represented by the
formula (18) include methylboronic acid, ethylboronic acid,
isopropylboronic acid, n-propylboronic acid, n-butylboronic acid,
isobutylboronic acid, n-hexylboronic acid, cyclohexylboronic acid,
phenylboronic acid, 3,5-difluorophenylboronic acid,
pentafluorophenylboronic acid and
3,5-bis(trifluoromethyl)phenylboronic acid. Of these, preferable
are methylboronic acid, n-butylboronic acid, isobutylboronic acid,
3,5-difluorophenylboronic acid and pentafluorophenylboronic acid.
These alkylboronic acids are used singly or in combination of two
or more kinds.
[0240] Examples of the organoaluminum compounds to be reacted with
the alkylboronic acid include the same organoaluminum compounds as
those given as examples of the organoaluminum compounds represented
by the formula (11) or (12).
[0241] Of those compounds, preferable are trialkylaluminums and
tricycloalkylaluminums, and particularly preferable are
trimethylaluminum, triethylaluminum and triisobutylaluminum. These
organoaluminum compounds are used singly or in combination of two
or more kinds.
[0242] The above organoaluminum oxy-compounds (B-3) are used singly
or in combination of two or more kinds.
(B-4) Compound which Reacts with the Group IV Transition Metal
Compound (A) to Form Ion Pair
[0243] Examples of the compounds (B-4) which react with the Group
IV transition metal compound (A) to form an ion pair include Lewis
acid, an ionic compound, a borane compound and a carborane compound
described in Japanese Patent Laid-Open Publication No. 501950/1989,
Japanese Patent Laid-Open Publication No. 502036/1989, Japanese
Patent Laid-Open Publication No. 179005/1991, Japanese Patent
Laid-Open Publication No. 179006/1991, Japanese Patent Laid-Open
Publication No. 207703/1991, Japanese Patent Laid-Open Publication
No. 207704/1991 and U.S. Pat. No. 5,321,106.
[0244] The Lewis acid is specifically a compound represented by
BR.sub.3 (R is a phenyl group which may have a subsitituent, such
as fluorine, a methyl group or a trifluoromethyl group, or
fluorine), and examples thereof include trifluoroboron,
triphenylboron, tris(4-fluorophenyl)boron,
tris(3,5-difluorophenyl)boron, tris(4-fluoromethylphenyl)boron,
tris(pentafluorophenyl)boron, tris(p-tolyl)boron,
tris(o-tolyl)boron, tris(3,5-dimethylphenyl)boron, trimethylboron
and triisobutylboron.
[0245] The ionic compound is, for example, a compound represented
by the following formula (19).
##STR00005##
[0246] In the above formula, R.sup.e+ is H.sup.+, carbenium cation,
oxonium cation, ammonium cation, phosphonium cation,
cycloheptyltrienyl cation, ferrocenium cation having a transition
metal, or the like. R.sup.f to R.sup.i may be the same as or
different from one another and are each an organic group,
preferably an aryl group or a substituted aryl group.
[0247] Examples of the carbenium cations include tri-substituted
carbenium cations, such as triphenylcarbenium cation,
tris(methylphenyl)carbenium cation and
tris(dimethylphenyl)carbenium cation.
[0248] Examples of the ammonium cations include trialkylammonium
cations, such as trimethylammonium cation, triethylammonium cation,
tri(n-propyl)ammonium cation, triisopropylammonium cation,
tri(n-butyl)ammonium cation and triisobutylammonium cation;
N,N-dialkylanilinium cations, such as N,N-dimethylanilinium cation,
N,N-diethylanilinium cation and N,N-2,4,6-pentamethylanilinium
cation; and dialkylammonium cations, such as diisopropylammonium
cation and dicyclohexylammonium cation.
[0249] Examples of the phosphonium cations include
triarylphosphonium cations, such as triphenylphosphonium cation,
tris(methylphenyl)phosphonium cation and
tris(dimethylphenyl)phosphonium cation.
[0250] Of the above cations, preferable as R.sup.e is carbenium
cation, ammonium cation or the like, and particularly preferable is
triphenylcarbenium cation, N,N-dimethylanilinium cation or
N,N-diethylanilinium cation.
[0251] Examples of carbenium salts include triphenylcarbenium
tetraphenylborate, triphenylcarbenium
tetrakis(pentafluorophenyl)borate, triphenylcarbenium
tetrakis(3,5-ditrifluoromethylphenyl)borate,
tris(4-methylphenyl)carbenium tetrakis(pentafluorophenyl)borate and
tris(3,5-dimethylphenyl)carbenium
tetrakis(pentafluorophenyl)borate.
[0252] Examples of ammonium salts include trialkyl substituted
ammonium salts, N,N-dialkylanilinium salts and dialkylammonium
salts.
[0253] Examples of the trialkyl substituted ammonium salts include
triethylammonium tetraphenylborate, tripropylammonium
tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate,
trimethylammonium tetrakis(p-tolyl)borate, trimethylammonium
tetrakis(o-tolyl)borate, tri(n-butyl)ammonium
tetrakis(pentafluorophenyl)borate, triethylammonium
tetrakis(pentafluorophenyl)borate, tripropylammonium
tetrakis(pentafluorophenyl)borate, tripropylammonium
tetrakis(2,4-dimethylphenyl)borate, tri(n-butyl)ammonium
tetrakis(3,5-dimethylphenyl)borate, tri(n-butyl)ammonium
tetrakis(4-trifluoromethylphenyl)borate, tri(n-butyl)ammonium
tetrakis(3,5-ditrifluoromethylphenyl)borate, tri(n-butyl)ammonium
tetrakis(o-tolyl)borate, dioctadecylmethylammonium
tetraphenylborate, dioctadecylmethylammonium
tetrakis(p-tolyl)borate, dioctadecylmethylammonium
tetrakis(o-tolyl)borate, dioctadecylmethylammonium
tetrakis(pentafluorophenyl)borate, dioctadecylmethylammonium
tetrakis(2,4-dimethylphenyl)borate, dioctadecylmethylammonium
tetrakis(3,5-dimethylphenyl)borate, dioctadecylmethylammonium
tetrakis(4-trifluoromethylphenyl)borate, dioctadecylmethylammonium
tetrakis(3,5-ditrifluoromethylphenyl)borate, and
dioctadecylmethylammonium.
[0254] Examples of the N,N-dialkylanilinium salts include
N,N-dimethylanilinium tetraphenylborate, N,N-dimethylanilinium
tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium
tetrakis(3,5-ditrifluoromethylphenyl)borate, N,N-diethylanilinium
tetraphenylborate, N,N-diethylanilinium
tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium
tetrakis(3,5-ditrifluoromethylphenyl)borate,
N,N-2,4,6-pentamethylanilinium tetraphenylborate, and
N,N-2,4,6-pentamethylanilinium
tetrakis(pentafluorophenyl)borate.
[0255] Examples of the dialkylammonium salts include
di(1-propyl)ammonium tetrakis(pentafluorophenyl)borate and
dicyclohexylammonium tetraphenylborate.
[0256] Further, ferrocenium tetrakis(pentafluorophenyl)borate, a
triphenylcarbenium pentaphenylcyclopentadienyl complex, a
N,N-diethylanilinium pentaphenylcyclopentadienyl complex, a borate
compound represented by the following formula (20) or (21), a
borate compound containing active hydrogen, which is represented by
the following formula (22), a borate compound containing a silyl
group, which is represented by the following formula (23), etc. can
be also mentioned.
##STR00006##
[0257] In the above formula, Et is an ethyl group.
##STR00007## [B-Qn(Gq(T-H)r)z].sup.-A.sup.+ (22)
[0258] In the formula (22), B is boron. G is a poly-linking
hydrocarbon radical, and preferred poly-linking hydrocarbon is an
alkylene, allylene, ethylene or alkalylene radical containing 1 to
20 carbon atoms. Preferred examples of G include phenylene,
bisphenylene, naphthalene, methylene, ethylene, propylene,
1,4-butadiene and p-phenylenemethylene. The number of linkages of
the poly-linking radical G is r+1, that is, one linkage is a
linkage to borate anion, and other linkages r of G are linkages to
(T-H) groups. A.sup.+ is a cation.
[0259] T in the formula (22) is O, S, NR.sup.j or PR.sup.j, and
R.sup.j is a hydrocarbanyl radical, a trihydrocarbanylsilyl
radical, a trihydrocarbanylgermanium radical or a hydride. q is an
integer of 1 or greater, preferably 1. The T-H group is --OH, --SH,
--NRH or --PR.sup.jH, and R.sup.j is a hydrocarbinyl radical of 1
to 18 carbon atoms, preferably 1 to 10 carbon atoms, or hydrogen. A
preferred R.sup.j group is alkyl, cycloalkyl, allyl, allylalkyl or
alkylallyl having 1 to 18 carbon atoms. --OH, --SH, --NR.sup.jH or
--PR.sup.jH may be, for example, any of --C(O)--OH,
--C(S)--SH--C(O)--NR.sup.jH and C(O)--PR.sup.jH. A most preferred
group having active hydrogen is --OH group. Q is hydride or
dihydrocarbylamide, preferably dialkylamide, halide,
hydrocarbyloxide, alkoxide, allyloxide, hydrocarbyl, substituted
hydrocarbyl radical, or the like. n+z is 4.
[0260] [B-Qn(Gq(T-H)r)z] in the formula (22) is, for example,
triphenyl(hydroxyphenyl)borate, diphenyl-di(hydroxyphenyl)borate,
triphenyl(2,4-dihydroxyphenyl)borate,
tri(p-tolyl)(hydroxyphenyl)borate,
tris(pentafluorophenyl)(hydroxyphenyl)borate,
tris(2,4-dimethylphenyl)(hydroxyphenyl)borate,
tris(3,5-dimethylphenyl)(hydroxyphenyl)borate,
tris[3,5-di(trifluoromethyl)phenyl](hydroxyphenyl)borate,
tris(pentafluorophenyl)(2-hydroxyethyl)borate,
tris(pentafluorophenyl)(4-hydroxylbutyl)borate,
tris(pentafluorophenyl)(4-hydroxylcyclohexyl)borate,
tris(pentafluorophenyl)[4-(4-hydroxyphenyl)phenyl]borate, or
tris(pentafluorophenyl)(6-hydroxy-2-naphthyl)borate. Most preferred
is tris(pentafluorophenyl)(4-hydroxyphenyl)borate. Compounds
wherein --OH group in the above borate compounds is replaced with
--NHR.sup.j (R.sup.j is methyl, ethyl or t-butyl) are also
preferable.
[0261] A.sup.+ that is a counter cation of the borate compound is
carbonium cation, tropylium cation, ammonium cation, oxonium
cation, sulfonium cation, phosphonium cation or the like. A cation
of a metal or a cation of an organic metal which itself is apt to
be reduced can be also mentioned. Examples of such cations include
triphenylcarbonium ion, diphenylcarbonium ion, cycloheptatrinium,
indenium, triethylammonium, tripropylammonium, tributylammonium,
dimethylammonium, dipropylammonium, dicyclohexylammonium,
trioctylammonium, N,N-dimethylammonium, diethylammonium,
2,4,6-pentamethylammonium, N,N-dimethlphenylammonium,
di(i-propyl)ammonium, dicyclohexylammonium, triphenylphosphonium,
triphosphonium, tridimethylphenylphosphonium,
tri(methylphenyl)phosphonium, triphenylphosphonium ion,
triphenyloxonium ion, triethyloxonium ion, pyrinium, silver ion,
gold ion, platinum ion, copper ion, palladium ion, mercury ion and
ferrocenium ion. Of these, ammonium ion is particularly
preferable.
[B-Qn(Gq(SiR.sup.kR.sup.lR.sup.m)r)z].sup.-A.sup.+ (23)
[0262] In the formula (23), B is boron. G is a poly-linking
hydrocarbon radical, and preferred poly-linking hydrocarbon is an
alkylene, allylene, ethylene or alkalylene radical containing 1 to
20 carbon atoms. Preferred examples of G include phenylene,
bisphenylene, naphthalene, methylene, ethylene, propylene,
1,4-butadiene and p-phenylenemethylene. The number of linkages of
the poly-linking radical G is r+1, that is, one linkage is a
linkage to borate anion, and other linkages r of G are linkages to
(SiR.sup.kR.sup.lR.sup.m) groups. A.sup.+ is a cation. Q is an
integer of 1 or greater, preferably 1.
[0263] R.sup.k, R.sup.l and R.sup.m in the formula (24) are each a
hydrocarbanyl radical, a trihydrocarbanylsilyl radical, a
trihydrocarbanylgermanium radical, a hydrogen radical, an alkoxy
radical, a hydroxyl radical or a halogen compound radical. R.sup.k,
R.sup.l and R.sup.m may be the same or different. Q is hydride or
dihydrocarbylamide, preferably dialkylamide, halide,
hydrocarbyloxide, alkoxide, allyloxide, hydrocarbyl, substituted
hydrocarbyl radical, or the like, more preferably pentafluorobenzyl
radical. n+z is 4.
[0264] [B-Qn(Gq(SiR.sup.kR.sup.lR.sup.m)r)z].sup.- in the formula
(23) is, for example, triphenyl(4-dimethylchlorosilylphenyl)borate,
diphenyl-di(4-dimethylchlorosilylphenyl)borate,
triphenyl(4-dimethylmethoxysilylphenyl)borate,
tri(p-tolyl)(4-triethoxysilylphenyl)borate,
tris(pentafluorophenyl)(4-dimethylchlorosilylphenyl)borate,
tris(pentafluorophenyl)(4-dimethylmethoxysilylphenyl)borate,
tris(pentafluorophenyl)(4-trimethoxysilylphenyl)borate, or
tris(pentafluorophenyl)(6-dimethylchlorosilyl-2-naphthyl)borate.
[0265] As A.sup.+ that is a counter cation of the borate compound,
the same cation as that of A.sup.+ in the formula (22) can be
mentioned.
[0266] Examples of the borane compounds include salts of anions,
such as decaborane, bis[tri(n-butyl)ammonium]nonaborate,
bis[tri(n-butyl)ammonium]decaborate,
bis[tri(n-butyl)ammonium]undecaborate,
bis[tri(n-butyl)ammonium]dodecaborate,
bis[tri(n-butyl)ammonium]decachlorodecaborate and
bis[tri(n-butyl)ammonium]dodecachlorododecaborate, and salts of
metallic borane anions, such as
tri(n-butyl)ammoniumbis(dodecahydridododecaborate)cobaltate(III)
and
bis[tri(n-butyl)ammonium]bis(dodecahydridododecaborate)nickelate
(III)
[0267] Examples of the carborane compounds include salts of anions,
such as 4-carbanonaborane, 1,3-dicarbanonaborane,
6,9-dicarbadecaborane,
dodecahydrido-1-phenyl-1,3-dicarbanonaborane,
dodecahydrido-1-methyl-1,3-dicarbanonaborane,
undecahydrido-1,3-dimethyl-1,3-dicarbononaborane,
7,8-dicarboundecaborane, 2,7-dicarbaundecaborane,
undecahydrido-7,8-dimethyl-7,8-dicarbaundecaborane,
dodecahydrido-11-methyl-2,7-dicarboundecaborane,
tri(n-butyl)ammonium 1-carbadecaborate, tri(n-butyl)ammonium
1-carbaundecaborate, tri(n-butyl)ammonium 1-carbadodecaborate,
tri(n-butyl)ammonium 1-trimethylsilyl-1-carbadecaborate,
tri(n-butyl)ammonium bromo-1-carbadodecaborate,
tri(n-butyl)ammonium 6-carbadecaborate, tri(n-butyl)ammonium
6-carbadecaborate, tri(n-butyl)ammonium 7-carbaundecaborate,
tri(n-butyl)ammonium 7,8-dicarbaundecaborate, tri(n-butyl)ammonium
2,9-dicarbaundecaborate, tri(n-butyl)ammonium
dodecahydrido-8-methyl-7,9-dicarbaundecaborate,
tri(n-butyl)ammonium dodecahydrido-8-ethyl-7,9-dicarbaundecaborate,
tri(n-butyl)ammonium undecahydrido-8-butyl-7,9-dicarbaundecaborate,
tri(n-butyl)ammonium undecahydrido-8-allyl-7,9-dicarbaundecaborate,
tri(n-butyl)ammonium
undecahydrido-9-trimethylsilyl-7,8-dicarbaundecaborate and
tri(n-butyl)ammonium undecahydrido-4,6-dibromo-7-carbaundacaborate;
and salts of metallic carborane anions, such as
tri(n-butyl)ammonium
bis(nonahydrido-1,3-dicarbanonaborate)cobaltate(III),
tri(n-butyl)ammonium
bis(undecahydrido-7,8-dicarbaundecaborate)ferrate(III),
tri(n-butyl)ammonium
bis(undecahydrido-7,8-dicarbaundecaborate)cobaltate(III),
tri(n-butyl)ammonium
bis(undecahydrido-7,8-dicarbaundecaborate)nickelate(III),
tri(n-butyl)ammonium
bis(undecahydrido-7,8-dicarbaundecaborate)cuprate(III),
tri(n-butyl)ammonium
bis(undecahydrido-7,8-dicarbaundecaborate)aurate(III),
tri(n-butyl)ammonium
bis(nonahydrido-7,8-dimethyl-7,8-dicarbaundecaborate)ferrate(III),
tri(n-butyl)ammonium
bis(nonahydrido-7,8-dimethyl-7,8-dicarbaundecaborate) chromate
(III), tri(n-butyl)ammonium
bis(tribromooctahydrido-7,8-dicarbaundecaborate)cobaltate(III),
tris[tri(n-butyl)ammonium]bis(undecahydrido-7-carbaundecaborate)
chromate(III),
bis[tri(n-butyl)ammonium]bis(undecahydrido-7-carbaundecaborate)manganate(-
IV),
bis[tri(n-butyl)ammonium]bis(undecahydrido-7-carbaundecaborate)cobalt-
ate(III) and
bis[tri(n-butyl)ammonium]bis(undecahydrido-7-carbaundecaborate)nickelate(-
IV).
[0268] Such compounds (B-4) which react with the Group 4 transition
metal compound (A) to form an ion pair as above can be used as a
mixture of two or more kinds.
[0269] As the component (B) for use in the present invention, a
commercially available MAO/toluene solution using the aforesaid
organoaluminum oxy-compound (B-3) and manufactured by Nippon
Aluminum Alkyls, Ltd., or the like is preferably used.
[0270] In the preparation of the olefin polymerization catalyst for
use in the present invention, a carrier can be used, when needed.
The carrier is usually an inorganic or organic compound and is a
granular or fine particulate solid. Examples of the inorganic
compounds include porous oxides, inorganic chlorides, clay, clay
minerals and ion-exchange layer compounds.
[0271] As the porous oxides, SiO.sub.2, Al.sub.2O.sub.3, MgO, ZrO,
TiO.sub.2, B.sub.2O.sub.3, CaO, ZnO, BaO, ThO.sub.2, and composites
or mixtures thereof can be used, and for example, natural or
synthetic zeolite, SiO.sub.2--MgO, SiO.sub.2--Al.sub.2O.sub.3,
SiO.sub.2--TiO.sub.2, SiO.sub.2--V.sub.2O.sub.5,
SiO.sub.2--Cr.sub.2O.sub.3 and SiO.sub.2--TiO.sub.2--MgO can be
used.
[0272] The octene (co)polymer (ii) is preferably prepared by
(co)polymerizing an .alpha.-olefin in the presence of such an
olefin polymerization catalyst as above.
[0273] An embodiment of a process for preparing the octene
(co)polymer (ii) is described below in detail.
[0274] In the present invention, polymerization reaction is carried
out in a hydrocarbon medium. Examples of the hydrocarbon media
include aliphatic hydrocarbons, such as propane, butane, pentane,
hexane, heptane, octane, decane, dodecane and kerosine; alicyclic
hydrocarbons, such as cyclopentane, cyclohexane and
methylcyclopentane; aromatic hydrocarbons, such as benzene, toluene
and xylene; halogenated hydrocarbons, such as ethylene chloride,
chlorobenzene and dichloromethane; and petroleum fractions, such as
gasoline, kerosine and gas oil. Further, olefins for use in the
polymerization are also employable.
[0275] In the present invention, polymerization is carried out in
the presence of such an olefin polymerization catalyst as above,
and in the polymerization, the Group IV transition metal compound
(A) is used in an amount of usually 10.sup.-8 to 1 gram atom/liter,
preferably 10.sup.-7 to 10.sup.-1 gram atom/liter, in terms of a
concentration of a transition metal atom in the polymerization
reaction system.
[0276] The component (B-1) is used in such an amount that the molar
ratio ((B-1)/M) of the component (B-1) to the transition metal atom
(M) in the component (A) becomes usually 0.01 to 5000, preferably
0.05 to 2,000. The component (B-2) is used in such an amount that
the molar ratio ((B-2)/M) of the component (B-2) to the transition
metal atom (M) in the component (A) becomes usually 100 to 25000,
preferably 500 to 10000. The component (B-3) is used in such an
amount that the molar ratio ((B-3)/M) of an aluminum atom in the
component (B-3) to the transition metal atom (M) in the component
(A) becomes usually 10 to 5000, preferably 20 to 2000. The
component (B-4) is used in such an amount that the molar ratio
((B-4)/M) of the component (B-4) to the transition metal atom (M)
in the component (A) becomes usually 1 to 50, preferably 1 to
20.
[0277] The temperature for the polymerization of olefin using such
an olefin polymerization catalyst is usually in the range of -50 to
+200.degree. C., preferably 0 to 180.degree. C. The polymerization
pressure is usually in the range of normal pressure to 10 MPa
(gauge pressure), preferably normal pressure to 5 MPa (gauge
pressure). The polymerization reaction can be carried out by any of
a batch process, a semi-continuous process and a continuous
process. Further, the polymerization can be carried out in two or
more steps which are different in the reaction conditions. The
molecular weight of the resulting olefin polymer can be controlled
by allowing hydrogen to exist in the polymerization system or by
changing the polymerization temperature.
[0278] The kinematic viscosity of the olefin polymer at 100.degree.
C. depends upon the molecular weight of the polymer. That is to
say, as the molecular weight is increased, the viscosity becomes
higher, and as the molecular weight is decreased, the viscosity
becomes lower, so that the kinematic viscosity at 100.degree. C. is
adjusted by the above molecular weight control. Moreover, by
removing a low-molecular weight component of the resulting polymer
by a hitherto publicly known method such as vacuum distillation,
the molecular weight distribution (Mw/Mn) of the resulting polymer
can be adjusted to not more than 1.8.
[0279] In the present invention, a fatty acid ester (iii) having a
kinematic viscosity at 100.degree. C. of not more than 20
mm.sup.2/s is contained. When the kinematic viscosity is in this
range, it becomes possible to add the fatty acid ester in a
sufficient amount for inhibiting swelling of a lubricating oil
sealing agent when the kinematic viscosity of the whole lubricating
oil composition is adjusted.
[0280] Although the fatty acid ester (iii) having a kinematic
viscosity at 100.degree. C. of not more than 20 mm.sup.2/s is not
specifically restricted, such a fatty acid ester consisting of only
carbon, oxygen and hydrogen as described below is used.
[0281] The fatty acid ester is, for example, a monoester prepared
from a monobasic acid and an alcohol; a diester prepared from a
dibasic acid and an alcohol, or prepared from diol and a monobasic
acid or an acid mixture; or a polyol ester prepared by the reaction
of diol, triol (e.g., trimethylolpropane), tetraol (e.g.,
pentaerythritol), hexaol (e.g., dipentaerythritol) or the like with
a monobasic acid or an acid mixture. Examples of such esters
include tridecyl pelargonate, di-2-ethylhexyl adipate,
di-2-ethylhexyl azelate, trimethylolpropane triheptanoate and
pentaerythritol tetraheptanoate.
[0282] From the viewpoint of compatibility with a 1-decene
(co)polymer or a 1-octene (co)polymer selected in the present
invention, the alcohol part to constitute the ester is preferably
an alcohol having two or more hydroxyl groups, and the fatty acid
part is preferably a fatty acid of 8 or more carbon atoms. As the
fatty acid, however, a fatty acid of 20 or less carbon atoms that
is industrially readily obtainable is advantageous from the
viewpoint of production cost. The fatty acid to constitute the
ester may be used singly, and even an acid mixture of two or more
kinds of fatty acids sufficiently exhibits the performance
disclosed in the present invention. More specifically,
trimethylolpropane lauric acid stearic acid mixed triester,
diisodecyl adipate, etc. can be mentioned, and these are preferable
from the viewpoint of compatibility with saturated hydrocarbon
components, such as a 1-decene (co)polymer and a 1-octene
(co)polymer, and the later-described stabilizers having a polar
group, such as an antioxidant, an anti-corrosion agent, an
anti-abrasion agent, a friction adjusting agent, a pour point
depressant, a rust proof agent and an anti-foaming agent.
[0283] The lubricating oil composition of the present invention
contains the decene (co)polymer (i) in an amount of 90 to 10% by
mass, preferably 80 to 20% by mass, the octene (co)polymer (ii) in
an amount of 5 to 85% by mass, and the ester (iii) in an amount of
5 to 15% by mass, with the proviso that the total amount of the
decene (co)polymer (i), the octene (co)polymer (ii) and the ester
(iii) is 100% by mass. When the decene (co)polymer (i), the octene
(co)polymer (ii) and the ester (iii) are contained in the above
ranges, a lubricating oil composition excellent in a balance
between the shear stability and the low-temperature viscosity
properties is obtained. By the addition of not less than 5% by mass
of the ester, good adaptability to lubricating oil sealing
materials such as resins or elastomers inside various internal
combustion engines and industrial machines is obtained.
Specifically, swelling of a lubricating oil sealing material can be
inhibited. From the viewpoint of oxidation stability or heat
resistance, the amount of the ester is preferably not more than 15%
by mass, with the proviso that the total amount of the components
(i) to (iii) is 100% by mass.
[0284] One characteristic of the lubricating oil composition of the
present invention is that it contains boron atoms in an amount of
not less than 5 ppm but not more than 75 ppm. A boron content of 1
ppm means that boron is contained in an amount of 1 mg in 1 kg of
the composition. It has been found by the present invention that
anti-micropitting performance of the lubricating oil composition is
particularly enhanced by introducing boron in the composition in a
specific concentration. It has been also found that performance of
the later-described extreme pressure agent that is optionally added
to the lubricating oil composition is sufficiently exhibited. The
boron atoms in the lubricating oil composition are derived from the
later-described boron compound. The content of the boron atoms in
the lubricating oil composition is measured by ICP emission
spectral analysis as in the later-described working examples.
[0285] As mechanism of exhibition of such effects, for example, the
following hypothesis can be considered.
[0286] At a gear part in an industrial machine or the like, the
surface convex portion of the frictional surface breaks through an
oil film of lubricating oil under the high-load conditions (also
referred to as "extreme pressure lubricating conditions") to cause
contact of metals, and because of increase in temperature of the
frictional surface due to the contact of metals and further because
of strong shear, the oil film is separated or removed from the
frictional surface. As a result, friction and abrasion are
increased, and this finally leads to seizing, resulting in a
possibility of impossible lubrication.
[0287] (On that account, it is preferable to add the
later-described extreme pressure agent capable of forming a reacted
film having larger affinity for a metal under the extreme pressure
lubricating conditions on the metal surface, to the lubricating oil
composition of the present invention. It is presumed that the film
formed by the extreme pressure agent on the metal surface is
effective also for improvement in durability against separation of
fine fragments from the gear tooth surface due to repeated
compression stress received at the gear part in the high-load
state, that is, micropitting.)
[0288] However, as described later, before the extreme pressure
lubricating conditions in which the extreme pressure agent forms a
film on the metal surface are reached, there is a possibility that
hydrocarbon or other organic components to constitute the
lubricating oil composition are carbonized by heating or shearing
to thereby form a carbide film on the metal surface.
[0289] It is considered that the boron-containing compound
interferes with a carbide or a carbide precursor prior to the
formation of the above-mentioned carbide film and functions as a
dispersing agent for preventing adhesion of a carbide to the metal
surface. Further, it is presumed that boron has affinity for metals
and therefore it bears a part of extreme pressure performance or
anti-abrasion performance.
[0290] It is thought that with regard to the micropitting, that is,
metal separation occurring particularly in the microscopic region,
the boron-containing compound is greatly concerned in metals, and
in the case of a boron atom content of not less than 5 ppm in the
lubricating oil composition, the lubricating oil composition
exhibits anti-micropitting performance. When long-term operation of
an engine is taken into account, the boron atom content is
preferably not less than 20 ppm. However, the boron-containing
compound has an extremely high polarity relatively to saturated
hydrocarbons such as a 1-decene (co)polymer and a 1-octene
(co)polymer which are main components of the lubricating oil
composition of the present invention, and therefore, from the
viewpoint of compatibility, the content of boron atoms needs to be
not more than 75 ppm, preferably not more than 50 ppm. It is
thought that if the boron atom content exceeds the upper limit of
this range, the boron-containing compound is aggregated because of
poor compatibility, and it inhibits low-temperature viscosity
properties of the lubricating oil composition, as an aggregate.
[0291] The boron-containing compound contained may be an organic
compound or an inorganic compound. In the inorganic compounds,
boron-containing acids, and their anhydrides, oxides and halides
are included. In the organic boron compounds, amides and esters of
boron are included. Further, borated acylated amine, a borated
dispersing agent, borated epoxide and borated fatty acid ester of
glycerol are also included.
[0292] Examples of the boron-containing compounds used include
boron oxide; boron oxide hydrate; boron trioxide; boron
trifluoride; boron tribromide; boron trichloride; and
boron-containing acids, such as boronic acid (i.e.,
alkyl-B(OH).sub.2 or aryl-B(OH).sub.2), boric acid (i.e.,
H.sub.3BO.sub.3), tetraboric acid (i.e., H.sub.2B4O.sub.7),
metaboric acid (i.e., HBO.sub.2) and boron containing acid
anhydride, and boron amides and various esters of such
boron-containing acids. A complex of a trihalide of boron and
ether, an organic acid or hydrocarbon is also employable. Examples
of such complexes include boron trifluoride-triethyl ester, boron
trifluoride-phosphoric acid, boron trichloride-chloroacetic acid,
boron tribromide-dioxane, and boron trifluoride methyl ethyl
ether.
[0293] From the viewpoint of compatibility with other components of
the lubricating oil composition, the boron-containing compound is
desirably an organic compound.
[0294] Examples of the boronic acids include methylboronic acid,
phenylboronic acid, cyclohexylboronic acid, p-heptylphenylboronic
acid and dodecylboronic acid. Examples of preferred
boron-containing compounds include boron oxides, such as boron
oxide, boron oxide hydrate and boron trioxide.
[0295] Examples of the boron containing acid esters include organic
monoesters, organic diesters and organic triesters of boric acid
and alcohols orphenols, such as methanol, ethanol, isopropanol,
butanol, pentanol, hexanol, cyclohexanol, cyclopentanol, 1-octanol,
2-octanol, dodecanol, behenyl alcohol, oleyl alcohol, stearyl
alcohol, benzyl alcohol, 2-butylcyclohexanol, ethylene glycol,
propylene glycol, trimethylene glycol, 1,3-butanediol,
2,4-hexanediol, 1,2-cyclohexanediol, 1,3-octanediol, glycerol,
pentaerythritol diethylene glycol, carbitol, cellosolve,
triethylene glycol, tripropylene glycol, phenol, naphthol,
p-butylphenol, o,p-diheptylphenol, n-cyclohexylphenol,
2,2-bis(p-hydroxyphenyl)propane, polyisobutene (molecular weight:
1,500)-substituted phenol, ethylene chlorohydrin, o-chlorophenol,
m-nitrophenol, 6-bromooctanol and 7-keto-decanol. Lower alcohols,
1,2-glycol and 1,3-glycol, that is, alcohols having about 8 or less
carbon atoms are useful for preparing the boron containing acid
esters.
[0296] The process for preparing boron containing acid esters is
already known, and for example, a process for preparing organic
triborates using reaction of boron trichloride with 3 mol of
alcohol or phenol or reaction of boron oxide with alcohol or phenol
can be mentioned. As another process, direct esterification of
tetraboric acid with 3 mol of alcohol or phenol can be mentioned.
As a further process, formation of cyclic alkylene borate using
direct esterification of, for example, boric acid with glycol can
be mentioned.
[0297] In a certain embodiment, the boron-containing compound is a
compound wherein an oil-soluble ash-free dispersing agent is
borated.
[0298] The ash-free dispersing agent has basic nitrogen and/or at
least one hydroxyl group in a molecule. By allowing basic nitrogen
and/or at least one hydroxyl group in the ash-free dispersing agent
to react with boron, a borated ash-free dispersing agent is
obtained. Examples of preferred dispersing agents include
alkenylsuccinic acid imide, alkenylsuccinic acid ester,
alkenylsuccinic acid ester amide, Mannich base, hydrocarbyl
polyamine and polymeric polyamine.
[0299] The alkenylsuccinic acid imide can be formed by a hitherto
publicly known method, such as a method of heating alkenylsuccinic
anhydride, acid, acid ester, acid halide or lower alkyl ester
together with polyamine containing at least one primary amino
group. The alkenylsuccinic anhydride can be readily formed by
heating a mixture of an olefin and maleic anhydride up to a
temperature of for example about 180 to 220.degree. C. This olefin
is a polymer or a copolymer of a lower monoolefin, such as
ethylene, propylene, 1-butene, isobutene or a mixture thereof. The
source of alkenyl group is, for example, polyisobutene having a gel
permeation chromatography (GPC) number-average molecular weight of
10,000 or more, for example, about 500 to about 2,500, or about 800
to about 1,500. In a certain embodiment, the molecular weight of
poyisobutylene is in the range of about 700 to about 5,000. The
ratio of polyisobutylenesuccinic anhydride to amine is, for
example, in the range of about 1.4 to about 3, or about 1.8 to
about 2.2.
[0300] In the lubricating oil composition of the present invention,
the above-mentioned boron-containing compounds may be used singly
or in combination of two or more kinds.
[0301] The lubricating oil composition of the present invention
preferably further contains one or more kinds of extreme pressure
agents.
[0302] The extreme pressure agent in the present application is a
component other than the components (i) to (iii), and is a general
term for substances exerting an effect in preventing sieving. The
extreme pressure agent is not specifically restricted, and examples
thereof include sulfur-based extreme pressure agents, such as
sulfides, sulfoxides, sulfones, thiophosphinates, thiocarbonates,
sulfurized fats and oils, and sulfurized olefins; phosphoric acids,
such as phosphoric acid ester, phosphorous acid ester, phosphoric
acid ester amine salt and phosphorous acid ester amines; and
halogen-based compounds, such as chlorinated hydrocarbon. These
compounds may be used in combination of two or more kinds.
[0303] However, before the extreme pressure lubricating conditions
are reached, there is a possibility that hydrocarbon or other
organic components to constitute the lubricating oil composition
are carbonized by heating or shearing to thereby form a carbide
film on the metal surface. On this account, when the extreme
pressure agent is used alone, there is a fear that the contact of
the extreme pressure agent with the metal surface is inhibited by
the carbide film and a satisfactory effect of the extreme pressure
agent cannot be expected.
[0304] In the addition of the boron-containing compound to the
lubricating oil composition, the boron-containing compound may be
added alone. However, the lubricating oil composition of the
present invention contains saturated hydrocarbons such as a
1-decene (co)polymer and a 1-octene (co)polymer as main components,
and therefore, from the viewpoint of dispersibility of the
boron-containing compound, it is preferable to add the
boron-containing compound in a dissolved state in lubricating base
oil such as mineral oil or 1-decene (co)polymer. In either method,
the boron-containing compound is added so that the boron atom
content may become not less than 5 ppm but not more than 75
ppm.
[0305] Specifically, it is more preferable that among so-called
extreme pressure agent packages in which various components such as
an extreme pressure component have been blended in advance, an
extreme pressure agent package in which the boron-containing
compound has been already added in a dissolved state is selected,
and this package is added to the lubricating oil composition.
[0306] In the case where the boron-containing compound is added in
a given amount as the extreme pressure agent package, it is
preferable to select the extreme pressure agent package containing
the boron-containing compound so that the amount of the extreme
pressure agent package added may become 2 to 5% by mass based on
100% by mass of the components (i) to (iii) in the lubricating oil
composition of the present invention. The extreme pressure agent
component is introduced into the extreme pressure agent package in
consideration of the concentration by which the extreme pressure
agent component can be sufficiently dispersed in the lubricating
oil composition, and therefore, if the amount of the extreme
pressure agent package is less than 2% by mass, a satisfactory
effect in the extreme pressure performance cannot be expected
occasionally, from the viewpoint of restriction on the upper limit
of the concentration. In contrast with this, if the amount thereof
exceeds 5% by mass, the boron-containing compound is aggregated
because of poor compatibility with the saturated hydrocarbon
components such as a 1-decene (co)polymer and a 1-octent
(co)polymer in the lubricating oil composition, and it sometimes
inhibits low-temperature viscosity properties of the lubricating
oil composition, as an aggregate.
[0307] Examples of preferred extreme pressure agents (packages)
include Anglamol 98A available from LUBRIZOL CORPORATION and HITEC
1532 available from AFTON CHEMICAL CORPORATION. In particular,
HITEC 307 available from AFTON CHEMICAL CORPORATION can be
preferably used from the viewpoint of a balance between the
boron-containing compound and other components.
[0308] The lubricating oil composition of the present invention may
further contain additives, such as a viscosity index improver, an
antioxidant, an anti-corrosion agent, an anti-abrasion agent, a
friction adjusting gent, a pour point depressant, a rust proof
agent and an anti-foaming agent.
[0309] As examples of the additives employable in the lubricating
oil composition of the present invention, the following compounds
can be given, and they can be used singly or in combination of two
or more kinds.
[0310] Examples of detergent dispersants include metallic
sulfonate, metallic phenate, metallic phosphanate and succinic acid
imide. The detergent dispersant is usually used in an amount of 0
to 15% by mass based on 100% by mass of the total amount of the
components (i) to (iii).
[0311] Examples of the anti-abrasion agents include inorganic or
organic molybdenum compounds such as molybdenum disulfide,
graphite, antimony sulfide and polytetrafluoroethylene. The
anti-abrasion agent is used in an amount of 0 to 3% by mass based
on 100% by mass of the total amount of the components (i) to (iii),
when needed.
[0312] Example of the antioxidants include phenol-based compounds
such as 2,6-di-tert-butyl-4-methylphenol, and amine-based
compounds. The anti-abrasion agent is used in an amount of 0 to 3%
by mass based on 100% by mass of the total amount of the components
(i) to (iii), when needed.
[0313] Examples of the rust proof agents include various amine
compounds, carboxylic acid metal salts, polyhydric alcohol esters,
phosphorus compounds and sulfonates. The rust proof agent is used
in an amount of 0 to 3% by mass based on 100% by mass of the total
amount of the components (i) to (iii), when needed.
[0314] Examples of the anti-foaming agents include silicone-based
compounds, such as dimethylsiloxane and a silica gel dispersion,
alcohol-based compounds and ester-based compounds. The anti-foaming
agent is used in an amount of 0 to 0.2% by mass based on 100% by
mass of the total amount of the components (i) to (iii), when
needed.
[0315] In addition to the above additives, a demulsifying agent, a
colorant, an oiliness agent (oiliness improver), etc. can be used,
when needed.
[0316] Since the lubricating oil composition of the present
invention uses a combination of the specific decene (co)polymer (i)
and the specific octene (co)polymer (ii), the composition is
excellent in shear stability. The shear stability is evaluated by a
KRL shear stability test based on the method described in Deutsche
Industrie Normen DIN 52350-6. Specifically, the lubricating oil
composition is allowed to stand at 60.degree. C. for 20 hours under
the shearing conditions (1450 rpm), and a kinematic viscosity
decrease ratio, that is obtained from a kinematic viscosity at
40.degree. C. after the test and a kinematic viscosity at
40.degree. C. before the test, is determined. As this value is
decreased, the shear stability of the rubricating oil composition
becomes more excellent. When the kinematic viscosity of the
lubricating oil composition of the present invention at 40.degree.
C. is adjusted to not less than 288 mm.sup.2/s but not more than
352 mm.sup.2/s, the kinematic viscosity decrease ratio of the
lubricating oil composition at 40.degree. C. after the KRL shear
stability test, as measured in accordance with DIN 52350-6, is
usually less than 10%, preferably less than 5%. A kinematic
viscosity at 40.degree. C. of not less than 288 mm.sup.2/s but not
more than 352 mm.sup.2/s indicates that this lubricating oil
composition has a viscosity grade (ISO 3448) of VG 320. The
lubricating oil composition having this viscosity grade is
particularly preferably used for gears for wind power
generators.
[0317] As described above, the lubricating oil composition of the
present invention contains the specific decene (co)polymer (i), the
specific octene (co)polymer (ii) and the specific ester (iii) and
contains boron atoms in a specific amount, and hence, the
composition is excellent in shear stability, low-temperature
viscosity properties and micropitting resistance and is also
excellent in a balance among oxidation stability, heat resistance
and temperature viscosity properties.
Uses
[0318] The lubricating oil composition of the present invention can
be used as industrial lubricating oil (gear oil, hydraulic oil) or
grease base oil. The lubricating oil composition of the present
invention is excellent in shear stability, low-temperature
viscosity properties and anti-micorpitting performance, as
described above, and hence, the composition is particularly
favorably used as lubricating oil for a wind power generator. If
the lubricating oil composition is excellent in the shear stability
and the anti-micropitting performance and if the composition is
used for a gear for a wind power generator, the gear can be
rendered maintenance-free. Moreover, also from the viewpoint of
efficiency of energy conversion from wind force into electric
power, it is preferable that the low-temperature viscosity
properties are excellent.
[0319] The gear for a wind power generator of the present invention
is lubricated with the above-mentioned lubricating oil
composition.
[0320] Each of FIGS. 1 to 4 shows an example of a wind power
generating apparatus having the gear for a wind power generator.
The wind power generating apparatus is provided with a planetary
gear (toothed wheel) type power transmission device, and
specifically has a rotor nose 1, an encasing opening 2, a roller
bearing 3, a rotor carrier 4, an azimuth bearing 5, an external
race 6, an internal race 7, a tow bin 8, a driving stage 9, a
driven stage 10, a generator 11, a sun gear 12, a hollow gear 13, a
hollow gear 14, a power transmission device casing 15, a planetary
gear carrier 16, a vibration damping device 17 and a fixed rail 18.
Functions and operations of these parts are the same as those
disclosed in Japanese Patent Laid-Open Publication No.
337245/2000.
[0321] The lubricating oil composition of the present invention is
favorably used for lubrication of the above gear part (toothed
wheel part).
[0322] As previously described, the present invention relates to
the following (1) to (7).
[0323] (1) A lubricating oil composition comprising the following
(i) to (iii), having a kinematic viscosity at 40.degree. C. of not
less than 30 mm.sup.2/s but not more than 750 mm.sup.2/s and
containing boron atoms in an amount of not less than 5 ppm but not
more than 75 ppm,
[0324] (i) 90 to 10% by mass of a (co)polymer having a kinematic
viscosity at 100.degree. C. of not more than 45 mm.sup.2/s,
containing not less than 60% by mol of constituent units derived
from 1-decene and having an acid value of less than 0.1
mgKOH/g,
[0325] (ii) 5 to 85% by mass of a (co)polymer having a kinematic
viscosity at 100.degree. C. of not less than 35 mm.sup.2/s but not
more than 1,500 mm.sup.2/s, containing not less than 90% by mol of
constituent units derived from 1-octene and having a molecular
weight distribution, as measured by gel permeation chromatography,
of not more than 1.8, and
[0326] (iii) 5 to 15% by mass of a fatty acid ester having a
kinematic viscosity at 100.degree. C. of not more than 20
mm.sup.2/s,
[0327] with the proviso that the total amount of (i) to (iii) is
100% by mass.
[0328] Since the above lubricating oil composition uses a
combination of the specific decene (co)polymer (i) and the specific
octene (co)polymer, the composition is excellent in shear
stability, low-temperature viscosity properties and temperature
viscosity properties. Further, since the boron content is in the
specific range, the lubricating oil composition is excellent in
anti-micropitting performance and low-temperature viscosity
properties.
[0329] (2) The lubricating oil composition as stated in (1), which
further comprises one or more kinds of extreme pressure agents.
[0330] (3) The lubricating oil composition as stated in (1) or (2),
wherein the kinematic viscosity of the lubricating oil composition
at 40.degree. C. is not less than 190 mm.sup.2/s but not more than
750 mm.sup.2/s.
[0331] When the kinematic viscosity at 40.degree. C. is not more
than 750 mm.sup.2/s, the lubricating oil composition is excellent
in fuel saving performance and energy conversion efficiency. When
the kinematic viscosity at 40.degree. C. is not less than 190
mm.sup.2/s, the lubricating oil composition exhibits good
lubricating properties and shear stability as gear oil at high
temperatures and/or in a high-load state.
[0332] (4) The lubricating oil composition as stated in any one of
(1) to (3), wherein the kinematic viscosity of the lubricating oil
composition at 40.degree. C. is not less than 288 mm.sup.2/s but
not more than 352 mm.sup.2/s, and a kinematic viscosity decrease
ratio of the lubricating oil composition at 40.degree. C. after a
KRL shear stability test, as measured in accordance with DIN
52350-6, is less than 10%.
[0333] When the lubricating oil composition is excellent in shear
stability as above, the composition is favorably used for a gear
for a wind power generator.
[0334] (5) The lubricating oil composition as stated in any one of
(1) to (4), wherein the kinematic viscosity of the octene
(co)polymer (ii) at 100.degree. C. is not less than 150 mm.sup.2/s
but not more than 1,200 mm.sup.2/s.
[0335] When the kinematic viscosity at 100.degree. C. is not less
than 150 mm.sup.2/s, the lubricating oil composition exhibits
excellent low-temperature viscosity properties. When the kinematic
viscosity at 100.degree. C. is not more than 1,200 mm.sup.2/s, the
shear stability of the lubricating oil composition is more
excellent.
[0336] (6) The lubricating oil composition as stated in any one of
(1) to (5), wherein the kinematic viscosity of the decene
(co)polymer (i) at 100.degree. C. is not more than 11
mm.sup.2/s.
[0337] When the kinematic viscosity at 100.degree. C. is not more
than 11 mm.sup.2/s, the low-temperature viscosity properties of the
lubricating oil composition are more excellent.
[0338] (7) A gear for a wind power generator, which is lubricated
with the lubricating oil composition as stated in any one of (1) to
(6).
[0339] Such a gear for a wind power generator can be rendered
maintenance-free and is excellent in efficiency of energy
conversion from wind force into electric power.
EXAMPLES
[0340] The present invention is further described with reference to
the following examples, but it should be construed that the present
invention is in no way limited to those examples.
Average Molecular Weight, Molecular Weight Distribution
[0341] Number-average molecular weight (Mn) and molecular weight
distribution (Mw/Mn) were measured in the following manner using
GPC (Chromatopac C-R4A) manufactured by Shimadzu Corporation. As
separation columns, TSKG6000H XL, G4000H XL, G3000H XL and G2000H
XL were used. The column temperature was set at 40.degree. C. As a
mobile phase, tetrahydrofuran (available from Wako Pure Chemical
Industries, Ltd.) was used. The developing rate was 0.8 ml/min, and
the sample concentration was 0.2% by mass. The sample injection
volume was 20 microliters, and as a detector, a differential
refractometer was used. As standard polystyrene, polystyrene
available from Tosoh Corporation was used.
Viscosity Properties
[0342] Kinematic viscosity at 100.degree. C. and at 40.degree. C.
and viscosity index were measured and calculated by the method
described in JIS K2283.
Shear Stability
[0343] Shear stability of a lubricating oil composition was
evaluated in accordance with the method described in DIN 52350-6
using a KRL shear stability tester. The compounded oil was allowed
to stand at 60.degree. C. for 20 hours under the shearing
conditions (1450 rpm). A kinematic viscosity at 40.degree. C. was
measured before and after the test, and a kinematic viscosity
decrease ratio after the test was evaluated.
[0344] When the kinematic viscosity decrease ratio is less than 10%
after a shear stress is given by the above method, the lubricating
oil composition exhibits good durability. When the kinematic
viscosity decrease ratio is less than 5%, the lubricating oil
composition exhibits extremely excellent durability.
-30.degree. C. Viscosity
[0345] -30.degree. C. Viscosity was measured by a Brookfield
viscometer in accordance with ASTM D2983. Taking error of
measurement into account, -30.degree. C. viscosities were
classified into the following three categories.
[0346] High: more than 100,000 mPas
[0347] Medium: more than 80,000 mPas but not more than 100,000
mPas
[0348] Low: not more than 80,000 mPas
[0349] When the -30.degree. C. viscosity is not more than 100,000
mPas, favorable lubricating properties can be maintained at
extremely low temperatures down to about -40.degree. C., and
excellent fuel saving performance and energy conversion efficiency
are exhibited. Particularly when the -30.degree. C. viscosity is
not more than 80,000 mPas, extremely excellent fuel saving
performance and energy conversion efficiency are exhibited. If the
-30.degree. C. viscosity exceeds 100,000 mPas, fuel saving
performance and energy conversion efficiency in an extremely low
temperature environment become poor.
Micropitting Failure Load Stage
[0350] Failure load stage was measured by a FVA-54/7 micropitting
test defined by Drive Technology Research Association (FVA). When
the failure load stage is not less than 10, excellent
anti-micropitting performance is exhibited.
(i) (Co)polymer Comprising 1-decene
[0351] As the decene (co)polymer (i) having a kinematic viscosity
at 100.degree. C. of not more than 45 mm.sup.2/s and comprising
1-decene, poly-.alpha.-olefin (PAO) available from NESTE OIL
CORPORATION, i.e., NEXBASE 2006 (kinematic viscosity at 100.degree.
C.: 6 mm.sup.2/s), was used. The acid value of the (co)polymer, as
measured in accordance with JIS K2501, was less than 0.1
mgKOH/g.
(ii) (Co)polymer Using 1-octene as Monomer
[0352] The octene (co)polymer (ii) using 1-octene as a monomer was
prepared by the following polymerization example.
[0353]
(Methyl)(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodib-
enzofluorenyl)zirconium dichloride used in the polymerization
example was synthesized by the following process.
Synthesis of 6,6'-methyl(p-tolyl)fulvene
[0354] In a 200 ml three neck flask, 5.9 g (81.9 mmol) of lithium
cyclopentadiene was placed in a nitrogen atmosphere, and 100 ml of
dehydrated diethyl ether was added, followed by stirring. The
resulting slurry was cooled with an ice bath, and 10.0 g (74.5
mmol) of 4'-methylacetophenone was dropwise added. Thereafter, the
mixture was stirred at room temperature for 20 hours, and the
resulting solution was quenched with a dilute hydrochloric acid
aqueous solution. Then, 50 ml of hexane was added, and the
resulting organic layer was washed with water and then dried over
anhydrous magnesium sulfate. The solvent was distilled off, and the
resulting viscous liquid was subjected to column chromatography
separation using hexane to obtain an object of a red viscous liquid
(yield: 9.8 g, 72%).
Synthesis of
(methyl)(p-tolyl)cyclopentadienyl(octamethyloctahydrodibenzofluorenyl)met-
hane
[0355] In a 200 ml three neck flask, 80 ml of tetrahydrofuran and
5.0 g (12.9 mmol) of octamethyloctahydrodibenzofluorene were mixed
in a nitrogen atmosphere, and the resulting solution was cooled to
-20.degree. C. Then, to the solution was slowly dropwise added 8.45
ml of n-butyllithium (1.61M hexane solution, 13.5 mmol), followed
by stirring at room temperature for 5 hours. Thereafter, this
reaction solution was cooled to -20.degree. C., and then 2.6 g
(14.2 mmol) of 6,6'-methyl(p-tolyl)fulvene was slowly dropwise
added. With slowly returning the temperature to room temperature,
the reaction solution was stirred for 1 hour. This reaction
solution was quenched with a dilute hydrochloric acid aqueous
solution and then extracted with diethyl ether. The resulting
organic layer was washed with a saturated sodium hydrogencarbonate
aqueous solution and a saturated saline solution, and then dried
over anhydrous magnesium sulfate. The solvent was distilled off,
and the resulting solid was recrystallized with methanol to obtain
a desired product of a white solid (yield: 7.2 g, 98%).
(iii) Ester
[0356] As the ester (iii) having a kinematic viscosity at
100.degree. C. of not more than 20 mm.sup.2/s, diisodecyl adipate
(DIDA) available from Daihachi Chemical Industry Co., Ltd., which
was a fatty acid ester, was used.
[0357] Extreme Pressure Agent Package
[0358] Extreme pressure agent A: As an extreme pressure agent
package having a boron content of 1,260 ppm, a commercially
available extreme pressure agent package (HITEC 307 available from
AFTON CHEMICAL CORPORATION) was used.
[0359] Extreme pressure agent B: As an extreme pressure agent
package having a boron content of less than 10 ppm, a commercially
available extreme pressure agent package (HITEC 343 available from
AFTON CHEMICAL CORPORATION) was used.
[0360] The boron content in the extreme pressure agent package was
measured by ICP emission spectral analysis. The boron content in
the lubricating oil composition was determined by converting the
boron content in the extreme pressure agent package and the amounts
of the components blended in the lubricating oil composition.
Polymerization Example 1
[0361] In a stainless steel autoclave having an internal volume of
2 liters and thoroughly purged with nitrogen, 1000 ml of 1-octene
was placed, and the temperature in the system was raised to
65.degree. C. Thereafter, hydrogen was fed to adjust the total
pressure to 3 MPa-G. Next, 0.4 mmol of triisobutylaluminum, 0.0007
mmol of a heptane solution of
di(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluor-
enyl)zirconium dichloride and 0.35 mmol (in terms of Al
concentration) of a hexane solution of methylaluminoxane (MMA0-3A,
available from Tosoh Finechem Corporation) were forced into the
autoclave with nitrogen, and polymerization was carried out at
70.degree. C. for 60 minutes at a rotation speed of 400 rpm. A
small amount of isopropanol was added to the system to terminate
the polymerization. After release of pressure, to the solution
taken out was added n-heptane, then the mixture was transferred
into a separatory funnel, and 100 ml of 1N hydrochloric acid was
added. The mixture was shaken and allowed to stand still for about
10 minutes, followed by performing oil-water separation. The
organic layer was withdrawn and then washed with water. To the
organic layer was added a small amount of sodium sulfate, and the
mixture was allowed to stand still for about 10 minutes to
dehydrate. Thereafter, the resulting solution was filtered to
remove sodium sulfate, and then n-heptane and unreacted 1-octene
were distilled off at 135.degree. C. under reduced pressure (300
mmHg). The amount of the resulting transparent liquid polymer
(1-octene polymer) was 83.7 g.
[0362] The molecular weight (Mn) of the resulting transparent
liquid 1-octene polymer (polymer 1), as measured by gel permeation
chromatography, was 6,450, and the distribution (Mw/Mn) was 1.67.
The kinematic viscosity, as measured by the method described in JIS
K2283, was 300 mm.sup.2/s at 100.degree. C. and was 3,750
mm.sup.2/s at 40.degree. C. The viscosity index, as calculated from
these kinematic viscosities, was 227.
Polymerization Example 2
[0363] In a stainless steel autoclave having an internal volume of
2 liters and thoroughly purged with nitrogen, 1000 ml of 1-octene
was placed, and the temperature in the system was raised to
45.degree. C. Thereafter, hydrogen was fed to adjust the total
pressure to 3 MPa-G. Next, 0.4 mmol of triisobutylaluminum, 0.001
mmol of a heptane solution of di(p-tolyl)methylene
(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium
dichloride and 0.50 mmol (in terms of Al concentration) of a hexane
solution of methylaluminoxane (MA0-3A, available from Tosoh
Finechem Corporation) were forced into the autoclave with nitrogen,
and polymerization was carried out at 50.degree. C. for 60 minutes
at a rotation speed of 400 rpm. A small amount of isopropanol was
added to the system to terminate the polymerization. After release
of pressure, to the solution taken out was added n-heptane, then
the mixture was transferred into a separatory funnel, and 100 ml of
1N hydrochloric acid was added. The mixture was shaken and allowed
to stand still for about 10 minutes, followed by performing
oil-water separation. The organic layer was withdrawn and then
washed with water. To the organic layer was added a small amount of
sodium sulfate, and the mixture was allowed to stand still for
about 10 minutes to dehydrate. Thereafter, the resulting solution
was filtered to remove sodium sulfate, and then n-heptane and
unreacted 1-octene were distilled off at 135.degree. C. under
reduced pressure (300 mmHg). The amount of the resulting
transparent liquid polymer (1-octene polymer) was 107.6 g.
[0364] The molecular weight (Mn) of the resulting transparent
liquid 1-octene polymer (polymer 2), as measured by gel permeation
chromatography, was 9,940, and the distribution (Mw/Mn) was 1.64.
The kinematic viscosity, as measured by the method described in JIS
K2283, was 640 mm.sup.2/s at 100.degree. C. and was 9,604
mm.sup.2/s at 40.degree. C. The viscosity index, as calculated from
these kinematic viscosities, was 253.
Polymerization Example 3
[0365] In a stainless steel autoclave having an internal volume of
2 liters and thoroughly purged with nitrogen, 1000 ml of 1-octene
was placed, and the temperature in the system was raised to
35.degree. C. Thereafter, hydrogen was fed to adjust the total
pressure to 3 MPa-G. Next, 0.4 mmol of triisobutylaluminum, 0.001
mmol of a heptane solution of
di(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluor-
enyl)zirconium dichloride and 0.50 mmol (in terms of Al
concentration) of a hexane solution of methylaluminoxane (MMA0-3A,
available from Tosoh Finechem Corporation) were forced into the
autoclave with nitrogen, and polymerization was carried out at
40.degree. C. for 60 minutes at a rotation speed of 400 rpm. A
small amount of isopropanol was added to the system to terminate
the polymerization. After release of pressure, to the solution
taken out was added n-heptane, then the mixture was transferred
into a separatory funnel, and 100 ml of 1N hydrochloric acid was
added. The mixture was shaken and allowed to stand still for about
10 minutes, followed by performing oil-water separation. The
organic layer was withdrawn and then washed with water. To the
organic layer was added a small amount of sodium sulfate, and the
mixture was allowed to stand still for about 10 minutes to
dehydrate. Thereafter, the resulting solution was filtered to
remove sodium sulfate, and then n-heptane and unreacted 1-octene
were distilled off at 135.degree. C. under reduced pressure (300
mmHg). The amount of the resulting transparent liquid polymer
(1-octene polymer) was 108.8 g.
[0366] The molecular weight (Mn) of the resulting transparent
liquid 1-octene polymer (polymer 3), as measured by gel permeation
chromatography, was 11,430, and the distribution (Mw/Mn) was 1.66.
The kinematic viscosity, as measured by the method described in JIS
K2283, was 920 mm.sup.2/s at 100.degree. C. and was 14,720
mm.sup.2/s at 40.degree. C. The viscosity index, as calculated from
these kinematic viscosities, was 269.
Polymerization Example 4
[0367] In a stainless steel autoclave having an internal volume of
2 liters and thoroughly purged with nitrogen, 300 ml of n-heptane
and 700 ml of 1-hexene were placed, and the temperature in the
system was raised to 75.degree. C. Thereafter, hydrogen was fed to
adjust the total pressure to 3 MPa-G. Next, 0.4 mmol of
triisobutylaluminum, 0.0015 mmol of a heptane solution of
di(p-tolyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluoreny-
l)zirconium dichloride and 0.75 mmol (in terms of Al concentration)
of a hexane solution of methylaluminoxane (MMA0-3A, available from
Tosoh Finechem Corporation) were forced into the autoclave with
nitrogen, and polymerization was carried out at 80.degree. C. for
60 minutes at a rotation speed of 400 rpm. A small amount of
isopropanol was added to the system to terminate the
polymerization. After release of pressure, to the solution taken
out was added n-heptane, then the mixture was transferred into a
separatory funnel, and 100 ml of 1N hydrochloric acid was added.
The mixture was shaken and allowed to stand still for about 10
minutes, followed by performing oil-water separation. The organic
layer was withdrawn and then washed with water. To the organic
layer was added a small amount of sodium sulfate, and the mixture
was allowed to stand still for about 10 minutes to dehydrate.
Thereafter, the resulting solution was filtered to remove sodium
sulfate, and then n-heptane and unreacted 1-hexene were distilled
off at 135.degree. C. under reduced pressure (300 mmHg). The amount
of the resulting transparent liquid polymer (1-hexene polymer) was
333.0 g.
[0368] The molecular weight (Mn) of the resulting transparent
liquid 1-hexene polymer (polymer 4), as measured by gel permeation
chromatography, was 3,900, and the distribution (Mw/Mn) was 1.73.
The kinematic viscosity, as measured by the method described in JIS
K2283, was 319 mm.sup.2/s at 100.degree. C. and was 6,296
mm.sup.2/s at 40.degree. C. The viscosity index, as calculated from
these kinematic viscosities, was 190.
Example 1
[0369] 33.2% by mass of the (co)polymer comprising 1-decene, 56.5%
by mass of the polymer 1 obtained in Polymerization Example 1 as
the (co)polymer using 1-octene as a monomer, 10.3% by mass of the
ester and 2.7% by mass of the extreme pressure agent A were
blended. The blending was controlled so that the kinematic
viscosity at 40.degree. C. would become 288 to 352 mm.sup.2/s.
Lubricating properties of the resulting lubricating oil composition
are set forth in Table 1.
Example 2
[0370] 45.5% by mass of the (co)polymer comprising 1-decene, 44.2%
by mass of the polymer 2 obtained in Polymerization Example 2 as
the (co)polymer using 1-octene as a monomer, 10.3% by mass of the
ester and 2.7% by mass of the extreme pressure agent A were
blended. The blending was controlled so that the kinematic
viscosity at 40.degree. C. would become 288 to 352 mm.sup.2/s.
Lubricating properties of the resulting lubricating oil composition
are set forth in Table 1.
Example 3
[0371] 49.7% by mass of the (co)polymer comprising 1-decene, 40.0%
by mass of the polymer 3 obtained in Polymerization Example 3 as
the (co)polymer using 1-octene as a monomer, 10.3% by mass of the
ester and 2.7% by mass of the extreme pressure agent A were
blended. The blending was controlled so that the kinematic
viscosity at 40.degree. C. would become 288 to 352 mm.sup.2/s.
Lubricating properties of the resulting lubricating oil composition
are set forth in Table 1.
Example 4
[0372] 45.4% by mass of the (co)polymer comprising 1-decene, 44.2%
by mass of the polymer 2 obtained in Polymerization Example 2 as
the (co)polymer using 1-octene as a monomer, 10.4% by mass of the
ester and 3.5% by mass of the extreme pressure agent A were
blended. The blending was controlled so that the kinematic
viscosity at 40.degree. C. would become 288 to 352 mm.sup.2/s.
Lubricating properties of the resulting lubricating oil composition
are set forth in Table 1.
Comparative Example 1
[0373] 32.3% by mass of the (co)polymer comprising 1-decene, 57.1%
by mass of the polymer 1 obtained in Polymerization Example 1 as
the (co)polymer using 1-octene as a monomer, 10.6% by mass of the
ester and 6.0% by mass of the extreme pressure agent A were
blended. The blending was controlled so that the kinematic
viscosity at 40.degree. C. would become 288 to 352 mm.sup.2/s.
Lubricating properties of the resulting lubricating oil composition
are set forth in Table 2.
Comparative Example 2
[0374] 23.6% by mass of the (co)polymer comprising 1-decene, 66.1%
by mass of Spectrasyn Ultra-150 available from ExxonMobil Chemical
Company as the (co)polymer using 1-decene as a monomer, 10.3% by
mass of the ester and 2.7% by mass of the extreme pressure agent A
were blended. The blending was controlled so that the kinematic
viscosity at 40.degree. C. would become 288 to 352 mm.sup.2/s.
Lubricating properties of the resulting lubricating oil composition
are set forth in Table 2.
Comparative Example 3
[0375] 34.0% by mass of the (co)polymer comprising 1-decene, 55.7%
by mass of Spectrasyn Ultra-300 available from ExxonMobil Chemical
Company as the (co)polymer using 1-decene as a monomer, 10.3% by
mass of the ester and 2.7% by mass of the extreme pressure agent A
were blended. The blending was controlled so that the kinematic
viscosity at 40.degree. C. would become 288 to 352 mm.sup.2/s.
Lubricating properties of the resulting lubricating oil composition
are set forth in Table 2.
Comparative Example 4
[0376] 51.2% by mass of the (co)polymer comprising 1-decene, 38.5%
by mass of Spectrasyn Ultra-1000 available from ExxonMobil Chemical
Company as the (co)polymer using 1-decene as a monomer, 10.3% by
mass of the ester and 2.7% by mass of the extreme pressure agent A
were blended. The blending was controlled so that the kinematic
viscosity at 40.degree. C. would become 288 to 352 mm.sup.2/s.
Lubricating properties of the resulting lubricating oil composition
are set forth in Table 2.
Comparative Example 5
[0377] Operations were carried out in accordance with Example 1,
except that the extreme pressure agent A was replaced with the
extreme pressure agent B. Lubricating properties of the resulting
lubricating oil composition are set forth in Table 2.
TABLE-US-00001 TABLE 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Content of PAO (i)
(% by mass) 33.2 45.5 49.7 45.4 Content of polymer (ii) (% by mass)
56.5 44.2 40.0 44.2 Content of ester (% by mass) 10.3 10.3 10.3
10.4 Content of extreme pressure agent 2.7 2.7 2.7 3.5 (% by mass)
Content of boron (ppm) 33 33 33 44 40.degree. C. Dynamic viscosity
(mm.sup.2/s) 325 326 329 328 -30.degree. C. Viscosity (mPa s)
medium low low medium Shear stability (dynamic viscosity 2.3 5.8
9.8 5.8 decrease ratio, %) Micropitting failure load stage >10
>10 >10 >10
TABLE-US-00002 TABLE 2 Comp. Comp. Comp. Comp Comp. Ex. 1 Ex. 2 Ex.
3 Ex. 4 Ex. 5 Content of PAO 32.3 23.6 34.0 51.2 33.2 (i) (% by
mass) Content of polymer 57.1 66.1 55.7 38.5 56.5 (ii) (% by mass)
Content of ester 10.6 10.3 10.3 10.3 10.3 (% by mass) Content of
extreme 6.0 2.7 2.7 2.7 2.7 pressure agent (% by mass) Content of
boron 76 33 33 33 <1 (ppm) 40.degree. C. Dynamic 326 315 320 319
325 viscosity (mm.sup.2/s) -30.degree. C. Viscosity high medium low
low medium (mPa s) Shear stability (dynamic 2.3 10.4 17.9 51 2.3
viscosity decrease ratio, %) Micropitting failure >10 >10
>10 >10 8 load stage
[0378] Polymerization Examples 1 to 3 are excellent in viscosity
index, namely, temperature viscosity properties, as compared with
the polymer using a monomer of 6 carbon atoms, i.e., 1-hexene, said
polymer being shown in Polymerization Example 4. Accordingly, it is
apparent that the low-temperature viscosity properties of the
lubricating oil composition of the present invention are superior
to those of the lubricating oil composition containing a polymer
using 1-hexene as a monomer.
[0379] Examples 1 to 4 (Table 1) are excellent in -30.degree. C.
viscosity as compared with Comparative Example 1 (Table 2) having a
boron content of more than 75 ppm.
[0380] Further, Examples 1 to 4 (Table 1) are excellent in shear
stability as compared with Comparative Examples 2 to 4 (Table 2) in
each of which a polymer using 1-decene as a monomer is contained in
the lubricating oil composition.
[0381] Furthermore, Examples 1 to 4 (Table 1) are excellent in
anti-micropitting performance as compared with Comparative Example
5 (Table 2) having a low boron content.
DESCRIPTION OF REFERENCE SIGNS
[0382] 1: rotor nose [0383] 2: encasing opening [0384] 3: roller
bearing [0385] 4: rotor carrier [0386] 5: azimuth bearing [0387] 8:
tow bin [0388] 9: driving stage [0389] 10: driven stage [0390] 11:
generator [0391] 12: sun gear [0392] 13: hollow gear [0393] 14:
hollow gear [0394] 15: power transmission device casing [0395] 16:
planetary gear carrier [0396] 17: vibration damping device [0397]
18: fixed rail
* * * * *