U.S. patent application number 10/250311 was filed with the patent office on 2004-03-25 for additive for lubricating oil and lubricating oil composition.
Invention is credited to Hirano, Hideki, Ito, Toshiyuki, Kan, Kojiro, Takeuchi, Kunihiko.
Application Number | 20040058830 10/250311 |
Document ID | / |
Family ID | 26624291 |
Filed Date | 2004-03-25 |
United States Patent
Application |
20040058830 |
Kind Code |
A1 |
Kan, Kojiro ; et
al. |
March 25, 2004 |
Additive for lubricating oil and lubricating oil composition
Abstract
The present invention is intended to provide a lubricating oil
additive having high viscosity index improvability and shear
stability and a lubricating oil composition containing the additive
and having excellent viscosity index and excellent shear stability.
The lubricating oil additive comprises an ethylene/.alpha.-olefin
random copolymer having the following properties: (i) said
copolymer is a copolymer of ethylene and at least one
.alpha.-olefin selected from .alpha.-olefins of 3 to 20 carbon
atoms and contains at least constituent units derived from ethylene
in amounts of 10 to 75% by mol and constituent units derived from
at least one .alpha.-olefin selected from .alpha.-olefins of 8 to
20 carbon atoms in amounts of 20 to 80% by mol, (ii) the kinematic
viscosity at 100.degree. C. is in the range of 500 to 1,000,000
mm.sup.2/s, (iii) the intrinsic viscosity [.eta.] is in the range
of 0.15 to 11.0 dl/g, (iv) the molecular weight distribution
(Mw/Mn), as measured by GPC, is not more than 4, and (v) the
number-average molecular weight is in the range of 5,000 to
30,000.
Inventors: |
Kan, Kojiro; (Sodegaura-shi,
Chiba, JP) ; Ito, Toshiyuki; (Sodegaura-shi, Chiba,
JP) ; Takeuchi, Kunihiko; (Sodegaura-shi, Chiba,
JP) ; Hirano, Hideki; (Sodegaura-shi, Chiba,
JP) |
Correspondence
Address: |
BURNS DOANE SWECKER & MATHIS L L P
POST OFFICE BOX 1404
ALEXANDRIA
VA
22313-1404
US
|
Family ID: |
26624291 |
Appl. No.: |
10/250311 |
Filed: |
June 30, 2003 |
PCT Filed: |
October 31, 2002 |
PCT NO: |
PCT/JP02/11366 |
Current U.S.
Class: |
508/591 |
Current CPC
Class: |
C10M 2205/026 20130101;
C10M 2205/003 20130101; C10N 2030/06 20130101; C10M 2205/022
20130101; C10M 2207/2805 20130101; C10M 2205/028 20130101; C10M
2205/024 20130101; C10N 2020/04 20130101; C10M 169/041 20130101;
C10M 2203/1006 20130101; C10N 2030/68 20200501; C10N 2030/08
20130101; C10M 143/08 20130101; C10N 2020/02 20130101; C10M 143/02
20130101; C10N 2030/02 20130101 |
Class at
Publication: |
508/591 |
International
Class: |
C10M 143/00 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 1, 2001 |
JP |
2001-336748 |
Aug 9, 2002 |
JP |
2002-233358 |
Claims
What is claimed is:
1. A lubricating oil additive comprising an ethylene/.alpha.-olefin
random copolymer having the following properties: (i) said
copolymer is a copolymer of ethylene and at least one
.alpha.-olefin selected from .alpha.-olefins of 3 to 20 carbon
atoms and contains at least constituent units derived from ethylene
in amounts of 10 to 75% by mol and constituent units derived from
at least one .alpha.-olefin selected from .alpha.-olefins of 8 to
20 carbon atoms in amounts of 20 to 80% by mol, (ii) the kinematic
viscosity at 100.degree. C. is in the range of 500 to 1,000,000
mm.sup.2/s, (iii) the intrinsic viscosity [.eta.], as measured in
decalin at 135.degree. C., is in the range of 0.15 to 1.0 dl/g,
(iv) the molecular weight distribution (Mw/Mn, Mw: weight-average
molecular weight, Mn: number-average molecular weight), as measured
by gel permeation chromatography, is not more than 4, and (v) the
number-average molecular weight is in the range of 5,000 to
30,000.
2. The lubricating oil additive as claimed in claim 1, wherein the
ethylene/.alpha.-olefin random copolymer contains constituent units
derived from ethylene in amounts of 30 to 75% by mol and
constituent units derived from at least one .alpha.-olefin selected
from .alpha.-olefins of 8 to 20 carbon atoms in amounts of 25 to
70% by mol.
3. The lubricating oil additive as claimed in claim 1, wherein the
ethylene/.alpha.-olefin random copolymer contains constituent units
derived from ethylene in amounts of 30 to 75% by mol and
constituent units derived from at least one .alpha.-olefin selected
from .alpha.-olefins of 10 to 16 carbon atoms in amounts of 25 to
70% by mol.
4. The lubricating oil additive as claimed in claim 1, wherein the
ethylene/.alpha.-olefin random copolymer contains constituent units
derived from ethylene in amounts of 35 to 70% by mol and
constituent units derived from 1-decene in amounts of 30 to 65% by
mol.
5. The lubricating oil additive as claimed in claim 1, wherein the
ethylene/.alpha.-olefin random copolymer contains constituent units
derived from ethylene in amounts of 10 to 75% by mol., constituent
units derived from at least one lower .alpha.-olefin selected from
.alpha.-olefins of 3 to 6 carbon atoms in amounts of 5 to 50% by
mol, and constituent units derived from at least one higher
.alpha.-olefin selected from .alpha.-olefins of 8 to 20 carbon
atoms in amounts of 20 to 85% by mol.
6. The lubricating oil additive as claimed in claim 1, wherein the
ethylene/.alpha.-olefin random copolymer contains constituent units
derived from ethylene in amounts of 10 to 70% by mol, constituent
units derived from at least one lower .alpha.-olefin selected from
.alpha.-olefins of 3 to 6 carbon atoms in amounts of 10 to 40% by
mol, and constituent units derived from at least one higher
.alpha.-olefin selected from .alpha.-olefins of 8 to 20 carbon
atoms in amounts of 20 to 80% by mol.
7. The lubricating oil additive as claimed in claim 1, wherein the
ethylene/.alpha.-olefin random copolymer contains constituent units
derived from ethylene in amounts of 10 to 70% by mol, constituent
units derived from at least one lower .alpha.-olefin selected from
.alpha.-olefins of 3 to 4 carbon atoms in amounts of 10 to 40% by
mol, and constituent units derived from at least one higher
.alpha.-olefin selected from .alpha.-olefins of 10 to 14 carbon
atoms in amounts of 20 to 80% by mol.
8. The lubricating oil additive as claimed in claim 1, wherein the
ethylene/.alpha.-olefin random copolymer contains constituent units
derived from ethylene in amounts of 10 to 70% by mol, constituent
units derived from propylene in amounts of 10 to 40% by mol, and
constituent units derived from 1-decene in amounts of 20 to 80% by
mol.
9. A lubricating oil additive containing constituent units derived
from ethylene in amounts of 30 to 75% by mol and constituent units
derived from at least one .alpha.-olefin selected from
.alpha.-olefins of 8 to 20 carbon atoms in amounts of 25 to 70% by
mol, and having the following properties: the shear stability (A
(%)) and the viscosity index (B) satisfy the following formula:
B.gtoreq.0.4.times.A+155, and A is a number satisfying the
condition of A.ltoreq.30.
10. The lubricating oil additive as claimed in claim 9, wherein the
shear stability (A (%)) and the low-temperature viscosity (C
(mPa.multidot.s)) as measured at -26.degree. C. satisfy the
following formula: C.ltoreq.-50.times.A+15,000.
11. A lubricating oil composition comprising: (A) at least one base
oil selected from a synthetic hydrocarbon, a mineral oil and an
ester, which has a kinematic viscosity at 100.degree. C. of 1 to 20
mm.sup.2/s, in an amount of 50 to 99.8 parts by weight, (B) the
lubricating oil additive of-any one of claims 1 to 10, in an amount
of 0.2 to 50 parts by weight, with the proviso that the total of
the component (A) and the component (B) is 100 parts by weight, and
optionally, (C) at least one additive selected from the group
consisting of a dispersant, a viscosity index improver, an
antioxidant, a corrosion inhibitor, an anti-wear agent, a pour
point depressant, a rust preventive, an anti-foaming agent and an
extreme pressure agent.
Description
TECHNICAL FIELD
[0001] The present invention relates to an ethylene/.alpha.-olefin
random copolymer useful as an additive having high viscosity index
and hardly suffering viscosity decrease attributable to permanent
or temporary shear, a lubricating oil composition containing the
copolymer.
BACKGROUND ART
[0002] An ethylene/propylene copolymer is well known as a
lubricating oil additive comprising an ethylene random copolymer.
Since this ethylene/propylene copolymer has no unsaturated double
bond and few tertiary carbon atoms, it exhibits excellent shear
stability and oxidation stability. Therefore, when this copolymer
is added-to a lubricating oil, such as gear oil, engine oil or
grease, the life of the oil is prolonged, and hence the copolymer
is widely employed.
[0003] Further, it is known that when the copolymer is added as a
thickening agent to a lubricating oil containing a synthetic
hydrocarbon or an ester as a base oil, the low-temperature
viscosity of the oil is decreased,(Japanese Patent Laid-Open
Publication No. 104695/1989).
[0004] However, the lubricating oil containing a mineral oil or a
hydrocarbon synthetic oil as a base oil and an ethylene/propylene
copolymer as a thickening agent has a viscosity index lower than
that of a lubricating oil containing PMA (polymethyl methacrylate).
On this account, the temperature dependence of the viscosity of the
lubricating oil is great, and if the high-temperature viscosity of
the lubricating oil is designed so as to be kept constant at a
certain value, the low-temperature viscosity is increased, and
therefore the use of the lubricating oil in winter or in the cold
district is sometimes restricted. Accordingly, a thickening agent
having high viscosity index improvability is desired.
[0005] The viscosity index improvability of an ethylene random
copolymer generally depends upon the molecular weight, and if the
molecular weight is increased, the viscosity index improvability is
also increased but the shear stability is decreased. If the
ethylene content is increased, the viscosity index improvability
and the shear stability are both enhanced, but the high-ethylene
content portion is crystallized to make the compounded oil turbid,
and hence the compounded oil cannot be used as a lubricating
oil.
[0006] On the other hand, it is generally known that PMA has high
viscosity index but has low shear stability.
[0007] Under such circumstances as mentioned above, the present
inventors have made various studies of the types and the amounts of
comonomers in ethylene random copolymers. As a result, they have
found that an ethylene/.alpha.-olefin random copolymer, which has
specific ranges of an .alpha.-olefin content, a kinematic viscosity
at 100.degree. C., an intrinsic viscosity [.eta.], and a molecular
weight distribution and a number-average molecular weight as
measured by gel permeation chromatography, has both of high
viscosity index improvability and excellent shear stability and is
favorable as an additive to a lubricating oil. That is to say, the
present inventors have found that an ethylene/.alpha.-olefin
copolymer having many branched chains of 6 or more carbon atoms has
both of high viscosity index improvability and excellent shear
stability.
[0008] In WO 01/85880A1, there is disclosed a viscosity modifier
for lubricating oil, which is a copolymer of ethylene, an
.alpha.-olefin of 3 or more carbon atoms and a higher
.alpha.-olefin of 4 to 20 carbon atoms whose number of carbon atoms
is larger by 1 or more than that of the .alpha.-olefin of 3, or
more carbon atoms, contains 40 to 80% by weight of ethylene, 15 to
59% by weight of the .alpha.-olefin of 3 or more carbon atoms and
0.1 to 25% by weight of the higher .alpha.-olefin of 4 to 20 carbon
atoms (total: 100% by weight), and has a weight-average molecular
weight of 80,000 to 400,000. This-copolymer, however, has an
.alpha.-olefin content lower than that of the
ethylene/.alpha.-olefin copolymer of the present invention.
[0009] It is an object of the present invention to provide a
lubricating oil additive having high viscosity index improvability
and shear stability and a lubricating oil, composition excellent in
viscosity index and shear stability.
DISCLOSURE OF THE INVENTION
[0010] According to the present invention, the following
lubricating oil thickening agent and lubricating oil composition
capable of attaining-the above object can be provided.
[0011] (1) A lubricating oil additive comprising an
ethylene/.alpha.-olefin random copolymer having the following
properties:
[0012] (i) said copolymer is a copolymer of ethylene and at least
one .alpha.-olefin selected from .alpha.-olefins of 3 to 20 carbon
atoms and contains at least constituent units derived from ethylene
in amounts of 10 to 75% by mol and constituent units derived from
at least one .alpha.-olefin selected from .alpha.-olefins of 8 to
20 carbon atoms in amounts of 20 to 80% by mol,
[0013] (ii) the kinematic viscosity at 100.degree. C. is in the
range of 500 to 1,000,000 mm.sup.2/s,
[0014] (iii) the intrinsic viscosity [.eta.], as measured in
decalin at 135.degree. C., is in the range of 0.15 to 1.0 dl/g,
[0015] (iv) the molecular weight distribution (Mw/Mn, Mw:
weight-average molecular weight, Mn: number-average molecular
weight), as measured by gel permeation chromatography, is not more
than 4, and
[0016] (v) the number-average molecular weight is in the range of
5,000 to 30,000.
[0017] (2) The lubricating oil additive as stated in the above (1),
wherein the ethylene/.alpha.-olefin random copolymer contains
constituent units derived from ethylene in amounts of 30 to 75% by
mol and constituent units derived from at least one .alpha.-olefin
selected from .alpha.-olefins of 8 to 20 carbon atoms in amounts of
25 to 70% by mol.
[0018] (3) The lubricating oil additive as-stated in the above (1),
wherein the ethylene/.alpha.-olefin random copolymer contains
constituent units derived from ethylene in amounts of 30 to 75% by
mol and constituent units derived from at least one .alpha.-olefin
selected from .alpha.-olefins of 10 to 16 carbon atoms in amounts
of 25 to 70% by mol.
[0019] (4) The lubricating oil additive as stated in the above (1),
wherein the ethylene/.alpha.-olefin random copolymer contains
constituent units derived from ethylene in amounts of 35 to 70% by
mol and constituent units derived from 1-decene in amounts of 30 to
65% by mol.
[0020] (5) The lubricating oil additive as stated in the above (1),
wherein the ethylene/.alpha.-olefin random copolymer contains
constituent units derived from ethylene in amounts of 10 to 75% by
mol, constituent units derived from at least one lower
.alpha.-olefin selected from .alpha.-olefins of 3 to 6 carbon atoms
in amounts of 5 to 50% by mol, and constituent units derived from
at least one higher .alpha.-olefin selected from .alpha.-olefins of
8 to 20 carbon atoms in amounts of 20 to 85% by mol.
[0021] (6) The lubricating oil additive as stated in the above (1),
wherein the ethylene/.alpha.-olefin random copolymer contains
constituent units derived from ethylene in amounts of 10 to 70% by
mol, constituent units derived from at least one lower
.alpha.-olefin selected from .alpha.-olefins of 3 to 6 carbon atoms
in amounts of 10 to 40% by mol, and constituent units derived from
at least one higher .alpha.-olefin selected from .alpha.-olefins of
8 to 20 carbon atoms in amounts of 20 to 80% by mol.
[0022] (7) The lubricating oil additive as stated in the above.(1),
wherein the ethylene/.alpha.-olefin random copolymer contains
constituent units derived from ethylene in amounts of 10 to. 70% by
mol, constituent units derived from at least one lower
.alpha.-olefin selected from .alpha.-olefins of 3 to 4 carbon atoms
in amounts of 10 to 40% by mol, and constituent units derived from
at least one higher .alpha.-olefin selected from .alpha.-olefins of
10 to 14 carbon atoms in amounts of 20 to 80% by mol.
[0023] (8) The lubricating oil additive as stated in the above (1),
wherein the ethylene/.alpha.-olefin random copolymer contains
constituent units derived from ethylene in amounts of 10 to 70% by
mol, constituent units derived from propylene in amounts of 10 to
40% by mol, and constituent units derived from 1-decene in amounts
of 20 to 80% by mol.
[0024] (9) A lubricating oil additive containing constituent units
derived from ethylene in amounts of 30 to 75% by mol and
constituent units derived from at least one .alpha.-olefin selected
from .alpha.-olefins of 8 to 20 carbon atoms in amounts of 25 to
70% by mol, and having the following properties:
[0025] the shear stability (A (%)) and the viscosity index (B)
satisfy the following formula:
B.gtoreq.0.4.times.A+155
[0026] and
[0027] A is a number-satisfying the condition of A.ltoreq.30.
[0028] (10) The lubricating oil additive as stated in the above
(9), wherein the shear stability (A (%)) and the low-temperature
viscosity (C (mPa.multidot.s)) as measured at -26.degree. C.
satisfy the following formula:
C.ltoreq.-50.times.A+15,000.
[0029] (11) A lubricating oil composition comprising:
[0030] (A) at least one base oil selected from a synthetic
hydrocarbon, a mineral oil and an ester, which has a kinematic
viscosity at 100.degree. C. of 1 to 20 mm.sup.2/s, in an amount of
50 to 99.8 parts by weight,
[0031] (B) the lubricating oil additive as stated in any one of the
above (1) to (10), in an amount of 0.2 to 50 parts by weight,
[0032] with the proviso that the total of the component (A) and the
component (B) is 100 parts by weight,
[0033] and optionally,
[0034] (C) at least one additive selected from the group consisting
of a dispersant, a viscosity index improver, an antioxidant, a
corrosion inhibitor, an anti-wear agent, a pour point depressant, a
rust preventive, an anti-foaming agent and an extreme pressure
agent.
BEST MODE FOR CARRYING OUT THE INVENTION
[0035] The lubricating oil additive and the lubricating oil
composition according to the invention are described in detail
hereinafter.
[0036] The lubricating oil additive according to the invention
comprises a liquid ethylene/.alpha.-olefin random copolymer.
[0037] The ethylene/.alpha.-olefin random copolymer is a copolymer
of ethylene and at least one .alpha.-olefin selected from
.alpha.-olefins of 3 to 20, carbon atoms and contains at least
constituent units derived from ethylene and Constituent units
derived from at least one .alpha.-olefin selected from
.alpha.-olefins of 8 to 20 carbon atoms.
[0038] The ethylene/.alpha.-olefin random copolymer that is a
lubricating oil thickening agent of the invention satisfies the
following requirements (i) to (v).
[0039] (i) The ethylene/.alpha.-olefin random copolymer contains
constituent units derived from ethylene in amounts of 10 to 75% by
mol and constituent units derived from at least one .alpha.-olefin
selected from .alpha.-olefins of 8 to 20 carbon atoms in amounts of
20 to 80% by mol.
[0040] In a preferred embodiment of the invention, the
ethylene/.alpha.-olefin random copolymer contains constituent units
derived from ethylene in amounts of 30 to 75%by mol, preferably 35
to 70% by mol, more preferably 50 to 70% by mol, and constituent
units derived from an .alpha.-olefin of 8 to 20 carbon atoms in
amounts of 25 to 70% by mol, preferably 30 to 65% by mol, more
preferably 30 to 50% by mol (copolymer (i-a))
[0041] In another preferred embodiment of the invention, the
ethylene/.alpha.-olefin random copolymer contains constituent units
derived from ethylene in amounts of 10 to 75% by mol, preferably 10
to 70% by mol, constituent units derived from at least one lower
.alpha.-olefin selected from .alpha.-olefins of 3 to 6 carbon atoms
in amounts of 10 to 50% by mol, preferably 10 to 40% by mol, and
constituent units derived from at least one higher .alpha.-olefin
selected from .alpha.-olefins of 8 to 20 carbon atoms in amounts of
20 to 85% by mol, preferably 20 to 80% by mol (copolymer
(i-b)).
[0042] Examples of the .alpha.-olefins of 3 to 6 carbon atoms
(lower .alpha.-olefins) include straight-chain .alpha.-olefins,
such as propylene, 1-butene, 1-pentene and 1-hexene, and branched
.alpha.-olefins, such as isobutylene, 3-methyl-1-butene and
4-methyl-1-pentene.
[0043] Examples of the .alpha.-olefins of 8 to 20 carbon atoms
(higher .alpha.-olefins) include straight-chain .alpha.-olefins,
such as 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene,
1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene,
1-octadecene, 1-nonadecene and 1-eicosene, and branched
.alpha.-olefins, such as 8-methyl-1-nonene, 7-methyl-1-decene,
6-methyl-1-undecene and 6,8-dimethyl-1-decene.
[0044] In the copolymer (i-a), the .alpha.-olefin of 8 to 20 carbon
atoms is preferably an .alpha.-olefin of 8 to 16 carbon atoms, more
preferably an .alpha.-olefin of 10 to 16 carbon atoms, still more
preferably an .alpha.-olefin of 10 to 12 carbon atoms, particularly
preferably 1-decene.
[0045] In the copolymer (i-a), two of more kinds of .alpha.-olefins
of 8 to 20 carbon atoms are employable, and for example, a
combination of 1-decene and 1-dodecene and a combination of
1-decene and 1-tetradecene are preferable.
[0046] In the copolymer (i-a), an .alpha.-olefin of 3 to 7 carbon
atoms may be copolymerized in a small amount (e.g., not more than
3% by mol).
[0047] In the copolymer (i-b), the lower .alpha.-olefin is
preferably an .alpha.-olefin of 3 or 4 carbon atoms, particularly
preferably propylene. In the copolymer (i-b), the higher
.alpha.-olefin is preferably an .alpha.-olefin of 8 to 16 carbon
atoms, more preferably an .alpha.-olefin of 10 to 14 carbon atoms,
still more preferably an .alpha.-olefin of 10 to 12 carbon atoms,
particularly preferably 1-decene.
[0048] In the copolymer (i-b)., two or more kinds of lower
.alpha.-olefins are employable, and two or more kinds of higher
.alpha.-olefins are employable.
[0049] When the ethylene content in the ethylene/.alpha.-olefin
random copolymer is in the above range, the copolymer has excellent
shear stability and high viscosity index improvability. Moreover,
the copolymer does not become turbid, and the pour point thereof
can be maintained low.
[0050] (ii) The kinematic viscosity at 100.degree. C. (JIS K 2283)
is in the range of 0.500 to 1,000,000 mm.sup.2/s, preferably 500 to
500,000 mm.sup.2/s, more preferably 1,000 to 100,000
mm.sup.2/s.
[0051] When the kinematic-viscosity of the ethylene/.alpha.-olefin
random copolymer at 100.degree. C. is in the above range, the
copolymer exhibits an excellent balance between the shear stability
and the viscosity index, so that it is practically desirable.
[0052] (iii) The intrinsic viscosity [i], as measured in decalin at
135.degree. C., is in the range of 0.15 to 1.0 dl/g, preferably
0.15 to 0.8 dl/g.
[0053] When the intrinsic viscosity [.eta.] of the
ethylene/.alpha.-olefin random copolymer is in the above range, the
copolymer exhibits an excellent balance between the shear stability
and the viscosity index, so that it is practically desirable.
[0054] (iv) The number-average molecular weight (Mn), as measured
by GPC (molecular weight standard substance: polystyrene), is in
the range of 5,000 to 30,000, preferably 5,000 to 27,000, more
preferably 8,000 to 27,000, still more preferably 10,000 to
25,000.
[0055] When the number-average molecular weight of the
ethylene/.alpha.-olefin random copolymer is in the above range, the
copolymer exhibits an excellent balance between the shear stability
and the viscosity index, so that it is practically desirable.
[0056] (v) The molecular weight distribution (Mw/Mn, Mw:
weight-average molecular weight, Mn: number-average molecular
weight), as measured by GPC, is not more than 4, preferably not
more than 3.5
[0057] When Mw/Mn of the ethylene/.alpha.-olefin random copolymer
is in the above range, the copolymer has excellent shear
stability.
[0058] When the ethylene/.alpha.-olefin random copolymer is the
copolymer (i-a), this copolymer can become a thickening agent
having high viscosity index improvability and shear stability. By
blending this thickening agent, a lubricating oil composition
excellent in viscosity index and shear stability and particularly
free from turbidity can be obtained.
[0059] When the ethylene/.alpha.-olefin random copolymer is the
copolymer (i-b), this copolymer can become a thickening agent
having high viscosity index improvability and shear stability. By
blending this thickening agent, a lubricating oil composition
excellent in viscosity index and shear stability and particularly
having a low pour point can be obtained.
[0060] The ethylene/.alpha.-olefin random copolymer of the
invention that is a lubricating oil thickening agent of the
invention preferably satisfies the above requirement (i) and the
following requirement (vi), or preferably satisfies the above
requirement (i) and the following requirements (vi) and (vii), or
preferably satisfies the above requirements (i) to (v) and the
following requirements (vi) and (vii). Such an
ethylene/.alpha.-olefin random copolymer is preferably the
copolymer (i-a).
[0061] (vi) The shear stability (A (%)) and the viscosity index (B)
satisfy the following formula:
B.gtoreq.0.4.times.A+155, and
[0062] A is a number satisfying the condition of A.ltoreq.30;
[0063] preferably, they satisfy the following formula:
B.gtoreq.0.4.times.A+158, and
[0064] A is a number satisfying the condition of A.ltoreq.25;
[0065] more preferably, they satisfy the following formula:
0.4.times.A+180.gtoreq.B.gtoreq.0.4.times.A+158, and
[0066] A is a number-satisfying the condition of A.ltoreq.22.
[0067] (vii) The shear stability (A (%)) and the low-temperature
viscosity (C (mPa.multidot.s)) as measured at -26.degree. C.
satisfy the following formula:
C.ltoreq.-50.times.A+15,000, and
[0068] A is a number satisfying the condition of A.ltoreq.30;
[0069] preferably, they satisfy the following formula:
C.ltoreq.-50.times.A+14,000, and
[0070] A is a number satisfying the condition of A.ltoreq.25;
[0071] more preferably, they satisfy the following formula:
-50.times.A+8,000.ltoreq.C.ltoreq.-50.times.A+14,000, and
[0072] A is a number satisfying the condition of A.ltoreq.20.
[0073] The ethylene/.alpha.-olefin random copolymer satisfying the
requirement (vi) and the ethylene/.alpha.-olefin random copolymer
satisfying the requirements (vi) and (vii) can each become a
thickening agent excellent in shear stability and low-temperature
viscosity properties.
[0074] Methods to measure the shear stability, the viscosity index
and the low-temperature viscosity are described later.
[0075] Process for Preparing Ethylene/.alpha.-Olefin Random
Copolymer
[0076] The ethylene/.alpha.-olefin random copolymer that is a
lubricating oil additive of the invention is desired to have a
structure wherein the .alpha.-olefin units are incorporated into
the polymer chain as uniformly as possible. Therefore, it is
preferable to prepare the copolymer by the use of a single site
catalyst system, and for example, it is preferable to prepare the
copolymer by the use of a metallocene catalyst consisting of a
metallocene compound and an organoaluminum oxy-compound and/or an
ionizing ionic compound. Examples of the metallocene catalysts
employable for the preparation of the ethylene/.alpha.-olefin
random copolymer are given below. As a matter of course, catalysts
other than the following ones are employable without any problem as
long as they can copolymerize .alpha.-olefins of 10 to 20 carbon
atoms with high randomness.
Metallocene Compound
[0077] The metallocene compound for constituting the metallocene
catalyst is a metallocene compound of a transition metal selected
from Group 4 of the periodic table and is, for example, a
compound-represented by the following formula (1):
ML.sub.x (1)
[0078] wherein M is a transition metal selected from the Group 4 of
the periodic table, x is a valence of the transition metal M, and L
is a ligand.
[0079] Examples of the transition metals indicated by M include
zirconium, titanium and hafnium. L is a ligand coordinated to the
transition metal. At least one ligand L is a ligand having
cyclopentadienyl skeleton, and the ligand having cyclopentadienyl
skeleton may have a substituent.
[0080] Examples of the ligands L having cyclopentadienyl skeleton
include cyclopentadenyl group; alkyl- or cycloalkyl-substituted
cyclopentadienyl groups, such as methylcyclopentadienyl,
ethylcyclopentadienyl, n- or i-propylcyclopentadienyl, n-, i-, sec-
or-t-butylcyclopentadienyl, dimethylcyclopentadienyl,
methylpropylcyclopentadienyl, methylbutylcyclopentadienyl and
methylbenzylcyclopentadienyl; indenyl group;
4,5,6,7-tetrahydtoindenyl group; and fluorenyl group. The hydrogen
in the group having cyclopentadienyl skeleton may be replaced with
a halogen atom or a trialkylsilyl group.
[0081] When the metallocene compound has two or more groups having
cyclopentadienyl skeleton as ligands L, two of the groups having
cyclopentadienyl skeleton may be bonded to each other through, for
example, an alkylene group, such as ethylene or propylene, a
substituted alkylene group, such as isopropylidene or
diphenylmethylene, a silylene group, or a substituted silylene
group, such as methylsilylene, diphenylsilylene or
methylphenylsilylene.
[0082] Examples of the ligands L (ligands L having no
cyclopentadienyl skeleton) other than the ligands having
cyclopentadienyl skeleton include a hydrocarbon group of 1 to 12
carbon atoms, an alkoxy group, an aryloxy group, a sulfonic
acid-containing group (--SO.sub.3R.sup.1) (R.sup.1 is an alkyl
group, an alkyl group substituted with a halogen atom, an aryl
group, or an aryl group substituted with a halogen atom or an alkyl
group), a halogen atom and a hydrogen atom.
Example 1 of the Metallocene Compound
[0083] The metallocene compound represented by the formula (1)
wherein the valence of the transition metal is 4 is more
specifically represented by the following formula (2):
R.sup.2.sub.kR.sup.3.sub.lR.sup.4.sub.mR.sup.5.sub.nM (2)
[0084] wherein M is a transition metal selected from Group 4 of-2
the periodic table, R is a group (ligand) having cyclopentadienyl
skeleton, R.sup.3, R.sup.4 and R.sup.5 are each independently a
group (ligand) having or not having cyclopentadienyl skeleton, k is
an integer of 1 or more, and k+l+m+n=4.
[0085] Examples of the metallocene compounds having zirconium as M
and containing at least two ligands having cyclopentadienyl
skeleton include bis(cyclopentadienyl)zirconium monochloride
monohydride, bis(cyclopentadienyl)zirconium dichloride,
bis(1-methyl-0.3-butylcyclopen-
tadienyl)zirconium-bis(trifluoromethanesulfonato),
bis(1,3-dimethylcyclope- ntadienyl)zirconium dichloride and
bis(n-butylcyclopentadienyl)zirconium dichloride.
[0086] Compounds wherein the 1,3-position substituted
cyclopentadienyl group in the above compounds is replaced with a
1,2-position substituted cyclopentadienyl group are also
employable.
[0087] As another example of the metallocene compound, a bridge
type metallocene compound of the formula (2) wherein at least two
of R.sup.2, R.sup.3, R.sup.4 and R.sup.5, for example, R.sup.2 and
R.sup.3, are each a group (ligand) having cyclopentadienyl
skeleton, and these at least two groups are bonded to each other
through an alkylene group, a substituted alkylene group, a silylene
group, a substituted silylene group or the like is also employable.
In this case, R.sup.4 and R.sup.5 are each independently identical
with the aforesaid ligand L other than the ligand having
cyclopentadienyl skeleton.
[0088] Examples of the bridge type metallocene compounds include
ethylenebis(indenyl)dimethylzirconium,
ethylenebis(indenyl)zirconium dichloride,
isopropylidene(cyclopentadienyl-fluoroenyl)zirconium dichloride,
diphenylsilylenebis(indenyl)zirconium dichloride and
methylphenylsilylenebis(indenyl)zirconium dichloride.
Example 2 of the Metallocene Compound
[0089] Another example of the metallocene compound is a metallocene
compound represented by the following formula (3), which is
described in Japanese Patent Laid-Open Publication No. 268307/1992.
1
[0090] In the above formula, M is a transition metal of Group 4 of
the periodic table, such as titanium, zirconium or hafnium.
[0091] R.sup.11 and R.sup.12 may be the same or different and are
each a hydrogen atom, an alkyl group of 1 to 10 carbon atoms, an
alkoxy group of 1 to 10 carbon atoms, an aryl group of 6 to 10
carbon atoms, an aryloxy group of 6 to 10 carbon atoms, an alkenyl
group of 2 to 10 carbon atoms, an arylalkyl group of 7 to 40 carbon
atoms, an alkylaryl group of 7 to 40 carbon atoms, an aryla-lkenyl
group of 8 to 40 carbon atoms, or a halogen atom, preferably a
chlorine atom.
[0092] R.sup.13 and R.sup.14 may be the same or different and are
each a hydrogen atom, a halogen atom, an alkyl group of 1 to -10
carbon atoms which may be halogenated, an aryl group of 6 to 10
carbon atoms, --N(R.sup.20)2 group, --SR.sup.20 group,
--OSi(R.sup.20).sub.3 group, --Si(R 20).sub.3 group or
--P(R.sup.20).sub.2 group. R.sup.20 is a halogen atom, preferably a
chorine atom, an alkyl group of 1 to 10 carbon atom, preferably 1
to 3 carbon atoms, or an aryl group of 6 to 10 carbon atoms,
preferably 6 to 8 carbon atoms. R.sup.13 and R.sup.14 are each
particularly preferably a hydrogen atom.
[0093] R.sup.15 and R.sup.16 are identical with R.sup.13 and
R.sup.14 except that a hydrogen atom is not included, and they may
be the same as or different from each other, preferably the same as
each other. R.sup.15 and R.sup.16 are each preferably an alkyl
group of 1 to 4 carbon atoms which may be halogenated, specifically
methyl, ethyl, propyl, isopropyl, butyl, isobutyl, trifluoromethyl
or the like, particularly preferably methyl.
[0094] In the formula (3), R.sup.17 is selected from the group
consisting of: 2
[0095] .dbd.BR.sup.21, AlR.sup.21, --Ge--, --Sn--, --O--, --S--,
.dbd.SO, .dbd.SO.sub.2, .dbd.NR, .dbd.CO, .dbd.PR.sup.21 and
.dbd.P(O)R.sup.21. M.sup.1 is silicon, germanium or tin, preferably
silicon or germanium.
[0096] In the above formulas, R.sup.21, R.sup.22 and R.sup.23 may
be the same or different and are each a hydrogen atom, a halogen
atom, an alkyl group of 1 to 10 carbon atoms, a fluoroalkyl group
of 1 to 10 carbon atoms, an aryl group of 6 to 10 carbon atoms, a
fluoroaryl group of 6 to 10 carbon atoms, an alkoxy group of 1 to
10 carbon atoms, an alkenyl group of 2 to 10 carbon atoms, an
arylalkyl group of 7 to 40 carbon atoms, an arylalkenyl group of 8
to 40 carbon atoms, or an alkylaryl group of 7 to 40 carbon atoms
"R.sup.21 and R.sup.22"or "R.sup.21 and R.sup.23" may form a ring
together with atoms to which they are bonded.
[0097] R.sup.17 is preferably .dbd.CR.sup.21R.sup.22,
.dbd.SiR.sup.21R.sup.22, .dbd.GeR.sup.2R.sup.22--O--, --S--,
.dbd.SO, .dbd.PR.sup.21 or .dbd.P(O)R.sup.21.
[0098] R.sup.18 and R.sup.19 may be the same or different and are
each the same group as indicated by R.sup.21.
[0099] m and n may be the same or different and are each 0, 1 or 2,
preferably 0 or 1. m+n is 0, 1 or 2, preferably 0 or 1.
[0100] Examples of the metallocene compounds represented by the
formula (3) include rac-ethylene(2-methyl-1-indenyl)
.sup.2_zirconium-dichloride,
rac-dimethylsilylene(2-methyl-1-indenyl).sup.2-zirconium-dichloride.
These metallocene compounds can be prepared by, for example, the
process described in Japanese Patent Laid-Open Publication No.
268307/1992.
Example 3 of the Metallocene Compound
[0101] As the metallocene compound, further, a metallocene compound
represented by the following formula (4) is-also employable. 3
[0102] In the above formula, M is a transition metal atom of Group
4 of the periodic table, specifically titanium, zirconium or
hafnium.
[0103] R.sup.24 and R.sup.25 may be the same or different and are
each a hydrogen atom, a halogen atom, a hydrocarbon group-of 1 to
20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon
atoms, a silicon-containing-group, an oxygen-containing group, a
sulfur-containing group, a nitrogen-containing group or a
phosphorus-containing group.
[0104] R.sup.24 is preferably a hydrocarbon group, particularly
preferably an alkyl group of 1 to 3 carbon atoms, such as methyl,
ethyl or propyl.
[0105] R.sup.25 is preferably a hydrogen atom or a hydrocarbon
group, particularly preferably a hydrogen atom or an alkyl group of
1 to 3 carbon atoms, such as methyl, ethyl or propyl.
[0106] R.sup.26, R.sup.27, R.sup.28 and R.sup.29 may be the same or
different and are each a hydrogen atom, a halogen atom, a
hydrocarbon group of 1 to 20 carbon atoms or a halogenated
hydrocarbon group of 1 to 20 carbon atoms. Of these, hydrogen, a
hydrocarbon group or a halogenated hydrocarbon group is preferable.
At least one combination of "R.sup.26 and R.sup.27", "R.sup.27 and
R.sup.28" and "R.sup.28 and R.sup.29 " may form a monocyclic
aromatic ring together with carbon atoms to which they are bonded.
When two or more kinds of hydrocarbon groups or halogenated
hydrocarbon groups are present in the groups other than the groups
for forming the aromatic ring, they may be bonded to each other to
form a ring. When R.sup.29 is a substituent other than the aromatic
group, it is preferably a hydrogen atom.
[0107] X.sup.1 and X.sup.2 may the same or different and are each a
hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20
carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon
atoms, an oxygen-containing group or a sulfur-containing group.
[0108] Y is a divalent hydrocarbon group of 1 to 20 carbon atoms, a
divalent halogenated hydrocarbon group of 1 to 20 carbon atoms, a
divalent silicon-containing group, a divalent germanium-containing
group, a divalent tin-containing group, --O--, --CO--, --S--,
--SO--, --SO.sub.2--, --NR.sup.30 P(R.sup.30)--,
--P(O)(R.sup.30)--, --BR.sup.30-- or --AlR.sup.30-- (R.sup.30 is a
hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20
carbon atoms or a halogenated hydrocarbon group of 1 to. 20 carbon
atoms).
[0109] Examples of the ligands, which contain a monocyclic aromatic
ring formed by bonding of at least one combination of "R.sup.26 and
R.sup.27", "R.sup.27 and R.sup.28" and "R.sup.28 and R.sup.29" and
are coordinated to M in the above formula, include ligands
represented by the following formulas: 4
[0110] wherein Y is the same as that in the above formula.
Example 4 of the Metallocene Compound
[0111] As the metallocene compound, further, a metallocene compound
represented by the following formula (5) is also employable. 5
[0112] In the above formula, M, R.sup.24, R.sup.25, R.sup.26
R.sup.27 R.sup.26 and R.sup.29 are the same as those in the formula
(4).
[0113] Of R.sup.26, R.sup.27, R.sup.28 and R.sup.29, two groups
including R.sup.26 are preferably alkyl groups, and R.sup.26 and
R.sup.27, or R.sup.28 and R.sup.29 are preferably alkyl groups.
These alkyl groups are each preferably a secondary or tertiary
alkyl group. These alkyl groups may be substituted with a halogen
atom or a silicon-containing group, and examples of the halogen
atoms and the silicon-containing groups include substituents
exemplified for R.sup.24 and R.sup.25.
[0114] Of R.sup.26, R.sup.27, R.sup.28 and R.sup.29, groups other
than the alkyl group are each preferably a hydrogen atom.
[0115] Two groups selected from R.sup.26, R.sup.27, R.sup.28 and
R.sup.29 may be bonded to each other to form a monocyclic or
polycyclic ring other than an aromatic ring. Examples of the
halogen atoms include the same atoms as described with respect to
R.sup.24 and R.sup.25.
[0116] X.sup.1, X.sup.2 and Y are the same as those previously
described.
[0117] Examples of the metallocene compounds represented by the
formula (5) include
rac-dimethylsilylene-bis(4,7-dimethyl-1-indenyl)zirconium
dichloride,
rac-dimethylsilylene-bis(2,4,7-trimethyl-1-indenyl)zirconium
dichloride and rac-dimethylsilylene-bis(2,4,6-trimethyl-1-indenyl)
zirconium dichloride.
[0118] Transition metal compounds wherein the zirconium metal in
the above compounds is replaced with a titanium metal or a hafnium
metal are also employable. Although the transition metal compound
is usually used as racemic modification, it may be used as R form
or S form.
Example 5 of the Metallocene Compound
[0119] As the metallocene compound, a metallocene compound
represented by the following formula (6) is also employable. 6
[0120] In the above formula, M, R.sup.2, .sup.4, X.sup.1, X.sup.2
and Y are each the same atom or group as described in the formula
(4).
[0121] R.sup.24 is preferably a hydrocarbon group, particularly
preferably an alkyl group of 1 to 4 carbon atoms, such as methyl,
ethyl, propyl or butyl.
[0122] R.sup.25 is an aryl group of 6 to 16 carbon atoms. R.sup.25
is preferably phenyl or naphthyl. The aryl group may be substituted
with a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms or
a halogenated hydrocarbon group of 1 to 20 carbon atoms.
[0123] X.sup.1 and X.sup.2 are each preferably a halogen atom or a
hydrocarbon group of 1 to 20 carbon atoms.
[0124] Examples of the metallocene compounds represented by the
formula (6) include
rac-dimethylsilylene-bis(4-phenyl-1-indenyl)zirconium dichloride,
rac-dimethylsilylene-bis(2-methyl-4-phenyl-1-indenyl)zirconiu- m
dichloride,
rac-dimethylsilylene-bis(2-methyl-4-((.alpha.-naphthyl)-1-in-
denyl)zirconium dichloride,
rac-dimethylsilylene-bis(2-methyl-4-(.beta.-na-
phthyl)-1-indenyl)zirconium dichloride and
rac-dimethylsilylene-bis(2-meth- yl-4-(l-anthryl)-1-indenyl)
zirconium dichloride. Transition metal compounds wherein the
zirconium metal in these compounds is replaced with a titanium
metal or a hafnium metal are also employable.
Example 6 of the Metallocene Compound
[0125] As the metallocene compound, further., a metallocene
compound represented by the following formula (7) is also
employable.
LaM.sup.2X.sup.3.sub.2 (7)
[0126] In the above formula, is a metal of Group 4 or lanthanide
series of the periodic table. La is a derivative of a delocalized
.pi. bond group and is a group imparting a constrained geometric
shape to the metal M.sup.2 active site. Each X.sup.3 may be the
same or different and is a hydrogen atom, a halogen atom, a
hydrocarbon group containing 20 or less carbon atoms, a silyl group
containing 20 or less silicon atoms, or a germyl group containing
20 or less germanium atoms of such compounds, a compound
represented by the following formula is preferable. 7
[0127] In the above formula, M.sup.2 is titanium, zirconium or
hafnium.
[0128] X.sup.3 is the same as that described in the formula
(7).
[0129] Cp is .pi. bonded to M.sup.2 and is a substituted
cyclopentadienyl group having a substituent Z.
[0130] Z is oxygen, sulfur, boron or an element of Group 4 of the
periodic table, such as silicon, germanium or tin.
[0131] Y is a ligand containing phosphorus, oxygen or sulfur, and Z
and Y may together form a condensed ring.
[0132] Examples of the metallocene compounds represented by the
above formula include (dimethyl(t-butylamido)
(tetramethyl-.eta..sup.5-cyclopen- tadienyl)silane)titanium
dichloride and ((t-butylamido)
(tetramethyl-.eta..sup.5-cyclopentadienyl)-1,2-ethanediyl)titanium
dichloride. Compounds wherein titanium is replaced with zirconium
or hafnium in these metallocene compounds are also employable.
Example 7 of the Metallocene Compound
[0133] As the metallocene compound, further, a metallocene compound
represented by the following formula (9) is also employable. 8
[0134] In the above formula, M is a transition metal atom of Group
4 of the periodic table, specifically titanium, zirconium or
hafnium, preferably zirconium.
[0135] Each R.sup.31 may be the same or different. At least one of
R.sup.3 is an aryl group of 11 to 20 carbon atoms, an arylalkyl
group of 12 to 40 carbon atoms, an arylalkenyl group of 13 to 40
carbon atoms, an alkylaryl group of 12 to 40 carbon atoms or a
silicon-containing group, or at least two neighboring groups of the
groups indicated by R.sup.31 form one or plural aromatic rings or
aliphatic rings together with carbon atoms to which they are
bonded. In this case, the ring formed by R.sup.31 has, in total, 4
to 20 carbon atoms including carbon atoms to which R.sup.31 is
bonded.
[0136] R.sup.31 other than R.sup.31 that forms an aryl group, an
arylalkyl group, an arylalkenyl group, an alkylaryl group and an
aromatic ring (or aliphatic ring) is a hydrogen atom, a halogen
atom, an alkyl group of 1 to 10 carbon atoms or a
silicon-containing group.
[0137] Each R.sup.32 may be the same or different and is a hydrogen
atom, a halogen atom, an alkyl group of 1 to 10 carbon atoms, an
aryl group of 6 to 20 carbon atoms, an alkenyl group of 2 to 10
carbon atoms, an arylalkyl group of 7 to 40 carbon atoms, an
arylalkenyl group of 8 to 40 carbon atoms, an alkylaryl group of 7
to 40 carbon atoms, a silicon-containing group, an
oxygen-containing group, a sulfur-containing group, a
nitrogen-containing group or a phosphorus-containing group.
[0138] Of the groups indicated by R.sup.32, at least two
neighboring groups may form one or plural aromatic rings or
aliphatic rings together with carbon atoms to which they are
bonded. In this case, the ring formed by R.sup.32 has, in total, 4
to 20 carbon atoms including carbon atoms to which R.sup.32 is
bonded. R.sup.32 other than R.sup.32 that forms an aromatic ring or
an aliphatic ring is a hydrogen atom, a halogen atom, an alkyl
group of 1 to 10 carbon atoms or a silicon-containing group.
[0139] The group, which is constituted by formation of one or
plural aromatic rings or aliphatic rings from two groups indicated
by R.sup.32, includes an embodiment wherein the fluorenyl group has
the following structure. 9
[0140] R.sup.32 is preferably a hydrogen atom or an alkyl group,
particularly preferably a hydrogen atom or a hydrocarbon group of 1
to 3 carbon atoms, such as methyl, ethyl or propyl. A preferred
example of the fluorenyl group having such a substituent R.sup.32
is a 2,7-dialkyl-fluroenyl group. In this case, the alkyl group of
the 2,7-dialkyl is, for example, an alkyl group of 1 to 5 carbon
atoms. R.sup.31 and R.sup.32 may be the same or different.
[0141] R.sup.33 and R.sup.34 may be the same or different and are
each the same hydrogen atom, halogen atom, alkyl group of 1 to 10
carbon atoms, aryl group of 6 to 20 carbon atoms, alkenyl group of
2 to 10 carbon atoms, arylalkyl group of 7 to 40 carbon atoms,
arylalkenyl group of 8 to 40 carbon atoms, alkylaryl group of 7 to
40 carbon atoms, silicon-containing group, oxygen-containing group,
sulfur-containing group, nitrogen-containing group or
phosphorus-containing group as previously described. At least one
of R.sup.33 and R.sup.34 is preferably an alkyl group of 1 to 3
carbon atoms.
[0142] X.sup.4 and X.sup.5 are the same or different and are each a
hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20
carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon
atoms, an oxygen-containing group, a sulfur-containing group, a
nitrogen-containing group, or a conjugated diene residue formed
from X.sup.4 and X.sup.5.
[0143] Preferred examples of the conjugated diene residues formed
from X.sup.4 and X.sup.5 include residues of 1,3-butadiene,
2,4-hexadiene, 1-phenyl-1,3-pentadiene and 1,4-diphenylbutadiene.
These residues may be substituted with a hydrocarbon group of 1 to
10 carbon atoms.
[0144] X.sup.4 and X.sup.5 are each preferably a halogen atom, a
hydrocarbon group of 1 to 20 carbon atoms or a sulfur-containing
group.
[0145] Y is a divalent hydrocarbon group of 1 to 20 carbon atoms, a
divalent halogenated hydrocarbon group of 1 to 20 carbon atoms, a
divalent silicon-containing group, a divalent germanium-containing
group, a divalent tin-containing group, --O--, --CO--, --S--,
--SO--, SO.sub.2--, --NR.sup.35--, P(R.sup.35)--,
--P(O)(R.sup.35)--, --BR.sup.35-- or --AlR.sup.35-- (R.sup.35 is a
hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20
carbon atoms or a halogenated hydrocarbon group of 1 to 20 carbon
atoms).
[0146] Of the above divalent groups, preferable is a group wherein
the shortest connecting portion of -Y- consists of one or two
atoms. R.sup.35 is a halogen atom, a hydrocarbon group of 1 to 20
carbon atoms or a halogenated hydrocarbon group of 1 to 20 carbon
atoms.
[0147] Y is preferably a divalent hydrocarbon group of 1 to 5
carbon atoms, a divalent silicon-containing group or a divalent
germanium-containing group, more preferably a divalent
silicon-containing group, particularly preferably alkylsilylene,
alkylarylsilylene or arylsilylene.
Example 8 of the Metallocene Compound
[0148] As the metallocene compound, further, a metallocene compound
represented by the following formula (10) is also employable.
10
[0149] In the above formula, M is a transition metal atom of Group
4 of the periodic table, specifically titanium, zirconium or
hafnium, preferably zirconium.
[0150] Each R.sup.36 may be the same or different and is a hydrogen
atom, a halogen atom, an alkyl group of 1 to 10 carbon atoms, an
aryl group of 6 to 10 carbon atoms, an alkenyl group of 2 to 10
carbon atoms, a silicon-containing group, an oxygen-containing
group, a sulfur-containing group, a nitrogen-containing group or a
phosphorus-containing group. The alkyl group and the alkenyl group
may be substituted with a halogen atom.
[0151] R.sup.36 is preferably an alkyl group, an aryl group or a
hydrogen atom, particularly preferably a hydrocarbon group of 1 to
3 carbon atoms, such as methyl, ethyl, n-propyl or i-propyl, an
aryl group, such as phenyl, .alpha.-naphthyl or .beta.-naphthyl, or
a hydrogen atom.
[0152] Each R.sup.37 may be the same or different and is a hydrogen
atom, a halogen atom, an alkyl group of 1 to 10 carbon atoms,
an-aryl group of 6 to 20 carbon atoms, an alkenyl group of 2 to 10
carbon atoms, an arylalkyl group of 7 to 40 carbon atoms, an
arylalkenyl group of 8 to 40 carbon atoms, an alkylaryl group of 7
to 40 carbon atoms, a silicon-containing group, an
oxygen-containing group, a sulfur-containing group, a
nitrogen-containing group or a phosphorus-containing group.
[0153] The alkyl group, the aryl group, the alkenyl group, the
arylalkyl group, the arylalkenyl group and the alkylaryl group may
be substituted with halogen.
[0154] R.sup.37 is preferably a hydrogen atom or an alkyl group,
particularly preferably a hydrogen atom or a hydrocarbon group of
i-to 4 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl,
n-butyl or tert-butyl. R.sup.36 and R.sup.37 may be the same or
different.
[0155] At least one of R.sup.38 and R.sup.39 is an alkyl group of 1
to 5 carbon atoms, and the other is a hydrogen atom, a halogen
atom, an alkyl group of 1 to 10 carbon atoms, an alkenyl group or 2
to 10 carbon atoms, a silicon-1.5 containing group, an
oxygen-containing group, a sulfur-containing group, a
nitrogen-containing group or a phosphorus-containing group.
[0156] It is preferable that at least one of R.sup.38 and R.sup.39
is an alkyl group of 1 to 3 carbon atoms, such as methyl, ethyl or
propyl and the other is a hydrogen atom.
[0157] X.sup.4 and X.sup.5 may be the same or different and are
each a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to
20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon
atoms, an oxygen-containing group, a sulfur-containing group, a
nitrogen-containing group, or a conjugated diene residue formed
from X.sup.4 and X.sup.5. Of these, preferable is a halogen atom or
a hydrocarbon group of 1 to 20 carbon atoms.
[0158] Y is a divalent hydrocarbon group of 1 to 20 carbon atoms, a
divalent halogenated hydrocarbon group of 1 to 20 carbon atoms, a
divalent silicon-containing group, a divalent germanium-containing
group, a divalent tin-containing group, --O--, --CO--, --S--,
--SO--, --SO.sub.2--, --NR.sup.40--, --P(R.sup.40)--,
--P(O)(R.sup.40)--, --BR.sup.40-- or --AlR.sup.40-- (R.sup.40 is a
hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 20
carbon atoms or a halogenated hydrocarbon group of 1 to 20 carbon
atoms).
[0159] Y is preferably a divalent hydrocarbon group of 1 to 5
carbon atoms, a divalent silicon-containing group or a divalent
germanium-containing group, more preferably a divalent
silicon-containing group, particularly preferably alkylsilylene,
alkylarylsilylene or arylsilylene.
[0160] The metallocene compounds mentioned above are used singly or
in combination of two or more kinds. The metallocene compounds may
be diluted with hydrocarbon, halogenated hydrocarbon or the like,
prior to use.
Organoaluminum Oxy-Compound
[0161] The organoaluminum oxy-compound may be aluminoxane publicly
known or may be a benzene-insoluble organoaluminum
oxy-compound.
[0162] Such publicly known aluminoxane is represented by any one of
the following formulas. 11
[0163] In the above formulas, R is a hydrocarbon group, such as
methyl, ethyl, propyl or butyl, preferably methyl or ethyl,
particularly preferably methyl, and m is an integer of 2 or more,
preferably an integer of 5 to 40.
[0164] The aluminoxane may be formed from mixed alkyloxyaluminum
units consisting of alkyloxyaluminum units represented by the
formula (OAl(R)) and alkyloxyaluminum units represented by the
formula (OAl(R")) (R' and R" are each the same hydrocarbon group as
exemplified for R, and R' and R" are groups different from each
other). The organoaluminum oxy-compound may contain a small amount
of an organic compound of a metal other than aluminum.
Ionizing Ionic Compound
[0165] The ionizing ionic compound (sometimes referred to as "ionic
ionizing compound" or "ionic compound") is, for example, Lewis
acid, an ionic compound, a borane compound or a carborane
compound.
[0166] The Lewis acid is, for example, a compound represented by
the formula BR.sub.3 (R is a phenyl group, which may have a
substituent such as fluorine, methyl or trifluoromethyl, or
fluorine). Examples of the Lewis acids 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 and tris(3,5-dimethylphenyl)boron.
[0167] The ionic compound is, for example, a trialkyl-substituted
ammonium salt, a N,N-dialkylanilinium salt, a dialkylammonium salt
or a triarylphosphonium salt. Examples of the trialkyl-substituted
ammonium salts as the ionic compounds include
triethylammoniumtetra(phenyl)boron,
tripropylammoniumtetra(phenyl)boron,
tri(n-butyl)ammoniumtetra(phenyl)bor- on. Examples of the
dialkylammonium salts as the ionic compounds include
di(l-propyl)ammoniumtetra(pentafluorophenyl)boron and
dicyclohexylammoniumtetra(phenyl)boron.
[0168] Also available as the ionic compounds are
triphenylcarbeniumtetraki- s(pentafluorophenyl)borate,
N,N-dimethylaniliniumtetrakis(pentafluoropheny- l)borate and
ferroceniumtetra(pentafluorophenyl)borate.
[0169] Examples of the borane compounds include decaborane(9), and
salts of metallic borane anions, such as
bis[tri(n-butyl)ammonium]nonaborate,
bis[tri(n-butyl)ammonium]decaborate and
bis[tri(n-butyl)ammonium]bis(dode-
cahydridododecaborate)niccolate(II I).
[0170] Examples of the carborane compounds include
4-carbanonaborane(9), 1,3-dicarbanonaborane(8), and salts of
metallic carborane anions, such as
bis[tri(n-butyl)ammonium]bis(undecahydrido-7-carbaundecaborate)niccolate(-
IV).
[0171] The ionizing ionic compounds-mentioned above are used singly
or in combination of two or more kinds. The organoaluminum
oxy-compound and the ionizing ionic compound may be used in the
supported form on the aforesaid carrier compounds.
[0172] In the preparation of the metallocene catalyst, the
following organoaluminum compound may be used together with the
organoaluminum oxy-compound and/or the ionizing ionic compound.
Organoaluminum Compound
[0173] As the organoaluminum compound that is used when needed, a
compound having at least one Al-carbon bond in the molecule is
employable. Examples of such compounds include:
[0174] an organoaluminum compound represented by the following
formula (11):
(R.sup.41).sub.mAl(OR.sup.42).sub.nH.sub.pX.sup.6.sub.q (11)
[0175] wherein R.sup.41 and R.sup.42 may the same or different and
are each a hydrocarbon group of usually 1 to 15 carbon atoms,
preferably 1 to 4 carbon atoms, X.sup.6 is a halogen atom, and m,
n, p and q are numbers satisfying conditions of 0<m.ltoreq.3,
0.ltoreq.n<3, 0.ltoreq.p<3, 0.ltoreq.q<3 and m+n+p+q=3;
and
[0176] an alkyl complex compound of a Group 1 metal and aluminum,
which is represented by the following formula (12):
(M.sup.3)Al(R.sup.41) (12)
[0177] wherein M.sup.3 is Li, Na or K, and R.sup.41 is the same as
R.sup.41 in the formula (11).
Polymerization
[0178] The ethylene/.alpha.-olefin random copolymer for use in the
invention can be prepared by, for example, copolymerizing ethylene
and an .alpha.-olefin of 3 to 20 carbon atoms in the presence of
the above-mentioned metallocene catalyst usually in a liquid phase.
Although a hydrocarbon solvent is generally used as a
polymerization solvent, an .alpha.-olefin may be used as the
solvent. The monomers used herein are those previously
described.
[0179] The copolymerization reaction may be carried out batchwise
or continuously. When the copolymerization is carried out
batchwise, the aforesaid catalyst components are used in the
following concentrations.
[0180] The concentration of the metallocene compound in the
polymerization system is in the range of usually 0.00005 to 0.1
mmol/l (polymerization volume), preferably 0.0001 to 0.05 mmol/l.
The organoaluminum oxy-compound is fed in such an amount that the
molar ratio (Al/transition metal) of the aluminum atom to the
transition metal in the metallocene compound in the polymerization
system becomes 1 to 10000, preferably 10 to 5000.
[0181] The ionizing ionic compound is fed in such an amount that
the molar ratio (ionizing ionic compound/metallocene compound) of
the ionizing ionic compound to the metallocene compound in the
polymerization system becomes 0.5 to 20, preferably 1 to 10.
[0182] The organoaluminum compound is used in an amount of usually
about 0 to 5 mmol/l (polymerization volume), preferably about 0 to
2 mmol/l.
[0183] The copolymerization reaction is carried out under the
conditions of a temperature of usually -20 to +150.degree. C.,
preferably 0 to-120.degree. C., more preferably 0 to 100.degree.
C., and a pressure of more than 0 MPa and not more than 7.8 MPa (80
kgf/cm.sup.2, gauge pressure), preferably more than 0 MPa and not
more than 4.9 MPa (50 kgf/cm.sup.2, gauge pressure).
[0184] In the copolymerization, ethylene and the .alpha.-olefin of
10 to 20 carbon atoms are fed in such amounts that an
ethylene/.alpha.-olefin random copolymer of the aforesaid specific
composition is obtained. In the copolymerization, further, a
molecular weight modifier such as hydrogen may be added.
Lubricating Oil Composition
[0185] The lubricating oil composition of the invention
comprises:
[0186] (A) at least one base oil selected from a synthetic
hydrocarbon, a mineral oil and an ester, which has a kinematic
viscosity at 100.degree. C. of 1 to 20 mm 2/s,
[0187] (B) the aforesaid ethylene/.alpha.-olefin random
copolymer,
[0188] and optionally,
[0189] (C) at least one additive selected from the group consisting
of a dispersant, a viscosity index improver, an antioxidant, a
corrosion inhibitor, an anti-wear agent, a pour point depressant.,
a rust preventive, an anti-foaming agent and an extreme pressure
agent.
Base Oil
[0190] The base oil used in the lubricating oil composition of the
invention has a kinematic viscosity at 100.degree. C. of 1 to 20
mm.sup.2/s and is selected from a synthetic hydrocarbon, a mineral
oil and an ester. As the synthetic hydrocarbon, the mineral oil and
the ester, those conventionally known are employed.
[0191] Examples of the synthetic hydrocarbons having a kinematic
viscosity at 100.degree. C. of 1 to 20 mm.sup.2/s include
.alpha.-olefin oligomers, alkylbenzenes and alkylnaphthalenes.
These can be used singly or in combination of two or more kinds. As
the .alpha.-olefin oligomer, a low-molecular weight oligomer of at
least one olefin selected from olefins of 8 to 12 carbon atoms is
employable. The .alpha.-olefin oligomer can be prepared by
polymerization using a Ziegler catalyst, thermal polymerization,
polymerization using free radical as a catalyst, or polymerization
using BF.sub.3 as a catalyst. Such polymerization processes are
described in, for example, U.S. Pat. No. 4,045,508.
[0192] Most of the alkylbenzenes or the alkylnaphtnalenes
employable as the base oil are usually dialkylbenzenes or
dialkylnaphthalenes wherein the alkyl chains have 6 to 14 carbon
atoms, and such dialkylbenzenes or alkylnaphthalenes are prepared
by Friedel-Crafts alkylation of benzene or naphthalene and olefin.
The alkylation olefin used in the preparation of the alkylbenzenes
or the alkylnaphthalenes may be a linear olefin, a branched olefin
or a combination thereof. The process for preparing them is
described in, for example, U.S. Pat. No. 3,909,432.
[0193] Examples of the esters having a kinematic viscosity at
100.degree. C. of 1 to 20 mm.sup.2/s include monoesters prepared
from monobasic acids such as pelargonic acid and alcohols; diesters
prepared from dibasic acids and alcohols or prepared from diols and
monobasic acids or acid mixtures; and polyol esters prepared by the
reaction of diols, triols (e.g., trimethylolpropane), tetraols
(e.g., pentaerythritol) or hexaols (e.g., dipentaerythritol) with
monobasic acids or acid mixtures. Particular examples of such
esters include tridecyl pelargonate, di-2-ethylhexyl adipate,
di-2-ethylhexyl azelate, trimethylolpropane triheptanoate and
pentaerythritol tetraheptanoate.
Other Additives
[0194] Examples of other additives, which can be added to the
lubricating oil composition of the invention when needed,
include:
[0195] detergents, such as neutral or basic sulfonates and phenates
(metal salt type);
[0196] dispersants, such as succinimide, esters, benzylamine and
copolymerization type polymers (ashless type);
[0197] pour point depressants, such as condensates of chlorinated
paraffin and naphthalene or phenol, polyalkyl acrylates, polyalkyl
methacrylates, polybutene, polyalkylstyrene and polyvinyl
acetate;
[0198] antioxidants, such as zinc thiophosphate and
trialkylphenol;
[0199] viscosity index improvers, such as high-molecular weight
ethylene/propylene copolymer and PMA;
[0200] emulsifying agents, such as sulfuric ester, sulfonic ester,
phosphoric ester, fatty acid derivatives, amine derivatives,
quaternary ammonium salt and polyoxyethylene type activators;
[0201] demulsifying agents, such as quaternary ammonium salt,
sulfonated oil and phosphoric ester;
[0202] antifungal substances, such as phenolic compounds,
formaldehyde donative compounds and salicylanilide type
compounds;
[0203] anti-stain agents;
[0204] untoucher agents;
[0205] anti-scorching agents; and
[0206] extreme pressure agents.
Composition
[0207] In the lubricating oil composition of the invention, the
content of the component (A) is in the range of 50 to 99.8 parts by
weight, preferably 60 to 95 parts by weight, and the content of the
component (B) is in the range of 0.2 to 50 parts by weight,
preferably 5 to 40 parts by weight, with the proviso that the total
of the component 0.20 (A) and the component (B) is 100 parts by
weight. The compounding ratio between the component (A) and the
component (B) is so determined that the resulting composition has a
kinematic viscosity of a prescribed value.
[0208] When the contents of the component (A) and the component (B)
are in the above ranges, an economical lubricating oil composition
having excellent shear stability, high viscosity index and low
low-temperature viscosity can be obtained.
[0209] The lubricating oil composition of the invention has high
viscosity index and shear stability and also has good appearance
without turbidity.
EFFECT OF THE INVENTION
[0210] The lubricating oil thickening agent according to the
invention has high viscosity index improvability and shear
stability.
[0211] The lubricating oil composition according to the invention
exhibits high viscosity index and shear stability and has good
appearance without turbidity.
EXAMPLE
[0212] The present invention is further described with reference to
the following examples, but it should be construed that the
invention is in no way limited to those examples.
[0213] The methods for evaluating the examples are as follows.
[0214] Kinematic Viscosity (mm.sup.2/s)
[0215] The kinematic viscosity was measured in accordance with JIS
K 2283.
[0216] Viscosity Index
[0217] The viscosity index was measured in accordance with JIS K
2283.
[0218] Intrinsic Viscosity [.eta.] (di/g)
[0219] The intrinsic viscosity was measured in decalin at
135.degree. C.
[0220] Number-Average Molecular Weight, Mw/Mn
[0221] The number-average molecular weight and Mw/Mn were measured
by GPC using polystyrene as a molecular weight standard
substance.
[0222] KRL shear stability (%)
[0223] A decrease (%) of the kinematic viscosity at 100.degree. C.
was measured in accordance with the CEC test method under the
conditions of 20 hours.
[0224] Pour point (.degree.C.)
[0225] The pour point was measured in accordance with JIS K
2269.
[0226] Low-temperature viscosity (mPa.multidot.s)
[0227] The viscosity at -26.degree. C. was measured in accordance
with ASTM D 2983.
[0228] Appearance
[0229] The appearance was visually observed, and a lubricating oil
composition free from turbidity was evaluated as good.
[0230] In the examples and the comparative examples, the following
copolymers were used.
[0231] Ethylene/1-decence copolymer (1)
[0232] ethylene content: 57% by mol, kinematic viscosity
(100.degree. C.): 361 mm.sup.2/S, [.eta.]: 0.120 dl/g, Mn: 8,600,
Mw/Mn: 1.7
[0233] Ethylene/1-decence copolymer (2)
[0234] ethylene content: 60% by mol, kinematic viscosity
(100.degree. C.): 730 mm.sup.2/S, [.eta.]: 0.165 dl/g, Mn: 10,700,
Mw/Mn: 1.6
[0235] Ethylene/1-decence copolymer (3)
[0236] ethylene content: 60% by mol, kinematic viscosity
(100.degree. C.): 1,440 mm.sup.2/s, [.eta.]: 0.190 dl/g, Mn:
13,400, Mw/Mn: 1.8
[0237] Ethylene/1-decence copolymer (4)
[0238] ethylene content: 66% by mol, kinematic viscosity
(100.degree. C.): 15,600 mm.sup.2/S, [.eta.]: 0.375 dl/g, Mn:
26,400, Mw/Mn: 1.8
[0239] Ethylene/1-octene copolymer (5)
[0240] ethylene content: 60% by mol, kinematic viscosity
(100.degree. C.): 1,460 mm.sup.2/s, [.eta.]: 0.180 dl/g, Mn:
10,600, Mw/Mn: 1.6
[0241] Ethylene/propylene/1-decence copolymer (6)
[0242] ethylene content: 65% by mol, propylene content: 5% by mol,
1-decene content: 30% by mol, kinematic viscosity (100.degree. C.):
3,030 mm.sup.2/s, [.eta.]: 0.240 dl/g, Mn: 16,100, Mw/Mn: 1.7
[0243] Ethylene/1-dodecene/1-tetradecence copolymer (7)
[0244] ethylene content: 65% by mol, 1-dodecene content: 20% by
mol, 1-tetradecene content: 15% by mol, kinematic viscosity
(100.degree. C.): 1,400 mm.sup.2/s, [.eta.]: 0.235 dl/g, Mn:
24,700, Mw/Mn: 1.6
[0245] Ethylene/propylene copolymer (8)
[0246] ethylene content: 50% by mol, kinematic viscosity
(100.degree. C.): 600 mm.sup.2/s, [.eta.]: 0.140 dl/g, Mn: 5,220,
Mw/Mn: 1.8.
[0247] Ethylene/propylene copolymer (9)
[0248] ethylene content: 50% by mol, kinematic viscosity
(100.degree. C.): 2,000 mm.sup.2/s, [.eta.]: 0.190 dl/g, Mn: 7,730,
Mw/Mn: 1.8
[0249] Ethylene/propylene copolymer (10)
[0250] ethylene content: 50% by mol, kinematic viscosity
(100.degree. C.): 15,600 mm.sup.2/s [.eta.]: 0.353 dl/g, Mn:
15,000, Mw/Mn: 1.9
[0251] Ethylene/1-decence copolymer-(11)
[0252] ethylene content: 65% by mol, [.eta.]: 0.50 dl/g, Mn:
52,000, Mw/Mn: 1.6
[0253] Ethylene/propylene/1-decence copolymer (12)
[0254] ethylene content: 65% by mol, propylene content: 15% by mol,
1-decene content: 20% by mol, [.eta.]: 0.170 dl/g, Mn: 11,500,
kinematic viscosity (100.degree. C.): 933 mm.sup.2/s, Mw/Mn:
1.6
[0255] Ethylene/propylene/1-decence-copolymer (13)
[0256] ethylene content: 65% by mol, propylene content: 15% by mol,
1-decene content: 20% by mol, [.eta.]: 0.240 dl/g, Mn: 16,100,
kinematic viscosity (100.degree. C.): 3,030 mm.sup.2/s, Mw/Mn:
1.7
[0257] Ethylene/1-butene/1-decence copolymer (14)
[0258] ethylene content: 50% by mol, 1-butene content: 15% by mol.
1-decene content: 35% by mol, [.eta.]: 0.202 dl/g, Mn: 14,400,
kinematic viscosity (100.degree. C.): 2,000 mm.sup.2/s, Mw/Mn:
1.7.
[0259] Ethylene/propylene/1-dodecence copolymer (15)
[0260] ethylene content: 65% by mol, propylene content: 15% by mol,
1-dodecene content: 20% by mol, [.eta.]: 0.220 dl/g, Mn: 16,000,
kinematic viscosity (100.degree. C.): 2,000 mm.sup.2/s, Mw/Mn:
1.7
[0261] Ethylene/propylene/1-decence copolymer (16)
[0262] ethylene content: 15% by mol, propylene content: 15% by mol,
1-decene content: 70% by mol, [.eta.]: 0.240 dl/g, Mn: 17,500,
kinematic viscosity (100.degree. C.): 4,000 mm.sup.2/s, Mw/Mn:
1.8
[0263] Ethylene/propylene copolymer (17)
[0264] ethylene content: 50% by mol, propylene content: 50% by mol,
[.eta.]: 0.190 dl/g, Mn: 7,700, kinematic viscosity (100.degree.
C.): 2,000 mm.sup.2/S, Mw/Mn: 1.9
[0265] Ethylene/1-decene copolymer (18)
[0266] ethylene content: 10% by mol, 1-decene content: 90% by mol,
[.eta.]: 0.200 dl/g, Mn: 16,500, kinematic viscosity (100.degree.
C.): 2,300 mm.sup.2/s, Mw/Mn: 2.0
[0267] Ethylene/propylene/1-decence copolymer (19)
[0268] ethylene content: 80% by mol, propylene content: 5% by mol,
1-decene content: 10% by mol, [.eta.]: 0.205 dl/g, Mn: 35,000,
kinematic viscosity (100.degree. C.): 2,100 mm.sup.2/s, Mw/Mn:
1.8
[0269] In the evaluations of the examples and the comparative
examples, the following base oil and additives were used.
[0270] Mineral oil (100N)
[0271] available from Fuji Kosan K.K., F-NT100 (100.degree. C.
kinematic viscosity: 4.29 mm.sup.2/S, viscosity index: 100)
[0272] Pour point depressant
[0273] available from Sanyo Kasei Kogyo K.K., ACLUBE 136, amount
added: 0.5%
[0274] Extreme pressure agent
[0275] available from Lubrizol, ANGRAMOL 98A, amount added:
6.5%
Examples 1 to 12, Comparative Examples 1 to 7
[0276] The components shown in Tables 1 to 4 were mixed in the
formulations (unit: g) shown in Tables 1 to 4 at 100.degree. C. for
1 hour, to obtain lubricating oil compositions. Evaluation results
of properties of the compositions are set forth in Tables 1 to
4.
1TABLE 1 Formulation Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7
Ethylene/1-decene copolymer (1) 18.6 Ethylene/1-decene copolymer
(2) 14.5 Ethylene/1-decene copolymer (3) 12.4 Ethylene/1-decene
copolymei (4) 6.7 Ethylene/1-octene copolymer (5) 12.5
Ethylene/propylene/1-dece- ne copolymer (6) 10.0
Ethylene/1-dodecene/1-tetradecene copolymer (7) 10.5 Pour point
depressant 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Extreme pressure agent 6.5
6.5 6.5 6.5 6.5 6.5 6.5 Mineral oil (100 N) 74.4 78.5 80.6 86.3
80.5 83.0 82.5 Compounded oil properties Kinematic viscosity
(mm.sup.2/s, at 40.degree. C.) 85.4 85.9 85.6 83.4 88.1 84.9 79.5
Kinematic viscosity (mm.sup.2/s, at 100.degree. C.) 14.0 14.0 14.1
14.2 14.1 13.99 13.85 Viscosity index 168 168 171 177 165 170 180
Low-temperature viscosity (mPa .multidot. s, at - 9,950 11,000
13,200 10,600 12,300 12,000 7,980 26.degree. C.) Shear stability
(viscosity decrease, %) 7.1 14.1 20.9 29.1 13.6 23.6 27.8
Appearance good good good good good good good
[0277]
2TABLE 2 Comp. Comp. Comp. Comp. Formulation Ex. 1 Ex. 2 Ex. 3 Ex.
4 Ethylene/propylene copolymer (8) 16.0 Ethylene/propylene
copolymer (9) 11.8 Ethylene/propylene copolymer (10) 6.6
Ethylene/1-decene copolymer (11) 5.0 Pour paint depressant 0.5 0.5
0.5 0.5 Extreme pressure agent 6.5 6.5 6.5 6.5 Mineral oil (100 N)
77.0 81.2 86.4 88.0 Compounded oil properties Kinematic viscosity
(mm.sup.2/s, 93.7 94.3 91.9 78.0 at 40.degree. C.) Kinematic
viscosity (mm.sup.2/s, 14.0 14.3 14.2 13.8 at 100.degree. C.)
Viscosity index 152 157 159 183 Low-temperature viscosity 13,200
15,600 14,700 7,980 (mPa .multidot. s, at -26.degree. C.) Shear
stability (viscosity decrease, 3.8 9.2 26.3 49.0 %) Appearance good
good good good
[0278]
3TABLE 3 Formulation Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12
Ethylene/propylene/1-decene copolymer (12) 13.8
Ethylene/propylene/1-decene copolymer (13) 11.5
Ethylene/1-butene/1-decene copolymer (14) 11.2
Ethylene/propylene/1-dodecene copolymer 11.0 (15)
Ethylene/propylene/1-decene copolymer (16) 10.1 PMA 0.5 0.5 0.5 0.5
0.5 Extreme pressure agent 6.5 6.5 6.5 6.5 6.5 Mineral oil (100 N)
79.2 83.0 81.8 82.0 82.9 Compounded oil properties Kinematic
viscosity (mm.sup.2/s, at 40.degree. C.) 86.93 84.87 83.36 82.90
82.92 Kinematic viscosity (mm.sup.2/s, at 100.degree. C.) 14.01
13.99 13.90 13.84 13.96 Viscosity index 166 170 172 172 174 Shear
stability (viscosity decrease, %) 9.1 10.6 12.8 10.1 20.5 Pour
point (.degree. C.) -42.5 -42.5 -42.5 -40 -42.5
[0279]
4TABLE 4 Comp. Comp. Comp. Formulation Ex. 5 Ex. 6 Ex. 7
Ethylene/propylene copolymer (17) 11.8 Ethylene/1-decene copolymer
(18) 12.0 Ethylene/propylene/1-decene copolymer (19) 11.4 PMA (pour
point depressant) 0.5 0.5 0.5 Extreme pressure agent 6.5 6.5 6.5
Mineral oil (100 N) 81.2 81.0 81.6 Compounded oil properties
Kinematic viscosity (mm.sup.2/s, at 40.degree. C.) 91.02 84.90
Kinematic viscosity (mm.sup.2/s, at 100.degree. C.) 14.01 13.83
Viscosity index 158 165 167 Shear stability (viscosity decrease, %)
9.2 32.1 9.0 Pour point (.degree. C.) -37.5 -35 -5
* * * * *