U.S. patent application number 09/860912 was filed with the patent office on 2002-01-24 for process for producing a polymer of an alpha-olefin and lubricant.
This patent application is currently assigned to Idemitsu Petrochemical Co., Ltd.. Invention is credited to Egawa, Tatsuya, Minami, Yutaka.
Application Number | 20020010290 09/860912 |
Document ID | / |
Family ID | 18664560 |
Filed Date | 2002-01-24 |
United States Patent
Application |
20020010290 |
Kind Code |
A1 |
Minami, Yutaka ; et
al. |
January 24, 2002 |
Process for producing a polymer of an alpha-olefin and
lubricant
Abstract
A process for producing a polymer of an .alpha.-olefin which
comprises polymerizing an .alpha.-olefin having at least 4 carbon
atoms in the presence of a catalyst for producing polymers of
olefins which comprises (A) a specific metal compound and (B) at
least one compound selected from (b-1) an organoaluminum oxy
compound and (b-2) an ionic compound. The polymer of an
.alpha.-olefin is useful as a component of lubricant.
Inventors: |
Minami, Yutaka; (Chiba-ken,
JP) ; Egawa, Tatsuya; (Chiba-ken, JP) |
Correspondence
Address: |
OBLON SPIVAK MCCLELLAND MAIER & NEUSTADT PC
FOURTH FLOOR
1755 JEFFERSON DAVIS HIGHWAY
ARLINGTON
VA
22202
US
|
Assignee: |
Idemitsu Petrochemical Co.,
Ltd.
Tokyo
JP
|
Family ID: |
18664560 |
Appl. No.: |
09/860912 |
Filed: |
May 21, 2001 |
Current U.S.
Class: |
526/127 ;
526/160; 526/348.2; 526/348.3; 526/348.4; 526/905; 526/943 |
Current CPC
Class: |
C10M 2205/028 20130101;
C10N 2020/01 20200501; C08F 110/14 20130101; C08F 4/65912 20130101;
Y10S 526/905 20130101; C10M 143/08 20130101; C08F 10/00 20130101;
C10M 107/10 20130101; C08F 10/00 20130101; C08F 4/63927 20130101;
C08F 110/14 20130101; C08F 2500/03 20130101; C08F 2500/17
20130101 |
Class at
Publication: |
526/127 ;
526/905; 526/160; 526/943; 526/348.2; 526/348.3; 526/348.4 |
International
Class: |
C08F 004/44 |
Foreign Application Data
Date |
Code |
Application Number |
May 30, 2000 |
JP |
2000-160355 |
Claims
What is claimed is:
1. A process for producing a polymer of an .alpha.-olefin which
comprises polymerizing an .alpha.-olefin having at least 4 carbon
atoms in a presence of a catalyst for producing polymers of olefins
which comprises: (A) at least one compound selected from transition
metal compounds represented by following general formulae (I) and
(II): 13 wherein R.sup.1 to R.sup.12 and X.sup.1 to X.sup.4 each
independently represent hydrogen atom, a halogen atom, a
hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group
having 1 to 20 carbon atoms and a halogen atom, a group having
silicon, a group having oxygen, a group having sulfur, a group
having nitrogen or a group having phosphorus; adjacent groups among
groups represented by R.sup.1 to R.sup.12 and X.sup.1 to X.sup.4
may form a ring by forming bonds between each other; three groups
represented by R.sup.9 may be the same with or different from each
other; three groups represented by R.sup.10 may be the same with or
different from each other; Y.sup.1 to Y.sup.4 each independently
represent a divalent group which forms a bond between two ligands
and is selected from hydrocarbon groups having 1 to 20 carbon
atoms, hydrocarbon groups having 1 to 20 carbon atom and a halogen
atom, a group having silicon, a group having germanium, a group
having tin, --O--, --CO--, --S--, --SO.sub.2--, --NR.sup.13--,
--PR.sup.13--, --P(O)R.sup.13--, --BR.sup.13-- and --AlR.sup.13--,
R.sup.13 representing hydrogen atom, a halogen atom, a hydrocarbon
group having 1 to 20 carbon atoms or a hydrocarbon group having 1
to 20 carbon atoms and a halogen atom, and M.sup.1 and M.sup.2 each
independently represent a transition metal of Groups 4 to 6 of the
Periodic Table; and (B) at least one compound selected from (b-1)
organoaluminum oxy compounds and (b-2) ionic compounds which can be
converted into cations by reaction with the transition metal
compounds of component (A).
2. A process according to claim 1, wherein the groups represented
by Y.sup.1 and Y.sup.2 in general formula (I) representing the
transition metal compound are each bonded to ligands in a meso
form.
3. A process according to claim 1, which comprises polymerizing an
.alpha.-olefin having at least 4 carbon atoms in a presence of
hydrogen.
4. A polymer of an .alpha.-olefin which is obtained in accordance
with a process described in claim 1 and has a weight-average
molecular weight in a range of 300 to 1,000,000.
5. A polymer of an .alpha.-olefin which is obtained by
hydrogenating a polymer of an .alpha.-olefin described in claim
4.
6. A lubricant which comprises a polymer of an .alpha.-olefin
described in claim 4.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a novel process for
producing a polymer of an .alpha.-olefin comprising polymerizing an
.alpha.-olefin having at least 4 carbon atoms and a lubricant
comprising the polymer.
[0003] 2. Description of the Related Arts
[0004] Various attempts have been made to obtain
poly-.alpha.-olefins which are useful as synthetic hydrocarbon
lubricant. For example, a process for polymerizing 1-decene in the
presence of a Friedel-Crafts catalyst which is aluminum chloride or
boron trifluoride is disclosed (U.S. Pat. Nos. 3,149,178 and
3,382,291).
[0005] However, the obtained poly-.alpha.-olefin has a low
molecular weight and the obtained lubricant had a low viscosity.
Moreover, boron trifluoride is not only expensive but also causes
an environmental problem since fluorine corroding apparatuses is
formed.
[0006] It has been disclosed that ethylene or an .alpha.-olefin is
polymerized in accordance with various processes and the obtained
polymer is used as a synthetic hydrocarbon lubricant. Examples of
such processes include a process in which a reduced chromium
catalyst is used (Japanese Patent Application (as a national phase
under PCT) Laid-Open No. Heisei 9(1997)-508151), a process in which
cation polymerization is conducted (Japanese Patent Application (as
a national phase under PCT) Laid-Open No. Heisei 8(1996)-505888), a
process in which a Ziegler-type catalyst is used (Japanese Patent
Application Laid-Open No. Heisei 7(1995)-145205 and Heisei
5(1993)-271339) and processes in which a metallocene catalyst is
used (Japanese Patent Application Laid-Open Nos. Heisei
7(1995)-133234 and Heisei 6(1994)-80725 and Japanese Patent Nos.
2796376 and 2664498). These processes have drawbacks in that an
expensive catalyst is used, that the activity of the polymerization
is small and that the use of ethylene is indispensable. Moreover,
products obtained in accordance with these processes have a
drawback in that the obtained polymer always has a low molecular
weight or the polymer having an extremely high molecular weight is
formed.
SUMMARY OF THE INVENTION
[0007] The present invention has an object of providing a novel
process for producing a polymer of an .alpha.-olefin comprising
polymerizing an .alpha.-olefin having at least 4 carbon atoms
efficiently and a lubricant comprising the polymer.
[0008] As the result of extensive studies by the present inventors
to achieve the above object, it was found that the above object can
be achieved by a process for producing a polymer of an
.alpha.-olefin which comprises polymerizing an .alpha.-olefin
having at least 4 carbon atoms in the presence of a catalyst for
producing polymers of olefins which comprises (A) a specific
transition metal catalyst and (B) at least one compound selected
from (b-1) organoaluminum oxy compounds and (b-2) ionic compounds
which can be converted into cations by reaction with the transition
metal compounds of component (A). The present invention has been
completed based on the knowledge.
[0009] The present invention provides:
[0010] (1) A process for producing a polymer of an .alpha.-olefin
which comprises polymerizing an .alpha.-olefin having at least 4
carbon atoms in a presence of a catalyst for producing polymers of
olefins which comprises:
[0011] (A) at least one compound selected from transition metal
compounds represented by following general formulae (I) and (II):
1
[0012] wherein R.sup.1 to R.sup.12 and X.sup.1 to X.sup.4 each
independently represent hydrogen atom, a halogen atom, a
hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group
having 1 to 20 carbon atoms and a halogen atom, a group having
silicon, a group having oxygen, a group having sulfur, a group
having nitrogen or a group having phosphorus; adjacent groups among
groups represented by R.sup.1 to R.sup.12 and X.sup.1 to X.sup.4
may form a ring by forming bonds between each other; three groups
represented by R.sup.9 may be the same with or different from each
other; three groups represented by R.sup.10 may be the same with or
different from each other; Y.sup.1 to Y.sup.4 each independently
represent a divalent group which forms a bond between two ligands
and is selected from hydrocarbon groups having 1 to 20 carbon
atoms, hydrocarbon groups having 1 to 20 carbon atom and a halogen
atom, a group having silicon, a group having germanium, a group
having tin, --O--, --CO--, --S--, --SO.sub.2--, --NR.sup.13--,
--PR.sup.13--, --P(O)R.sup.13--, --BR.sup.13-- and --AlR.sup.13--,
R.sup.13 representing hydrogen atom, a halogen atom, a hydrocarbon
group having 1 to 20 carbon atoms or a hydrocarbon group having 1
to 20 carbon atoms and a halogen atom, and M.sup.1 and M.sup.2 each
independently represent a transition metal of Groups 4 to 6 of the
Periodic Table; and
[0013] (B) at least one compound selected from (b-1) organoaluminum
oxy compounds and (b-2) ionic compounds which can be converted into
cations by reaction with the transition metal compounds of
component (A);
[0014] (2) A process described in (1), wherein the groups
represented by Y.sup.1 and Y.sup.2 in general formula (I)
representing the transition metal compound are each bonded to
ligands in a meso form;
[0015] (3) A process described in any of (1) and (2), which
comprises polymerizing an .alpha.-olefin having at least 4 carbon
atoms in a presence of hydrogen;
[0016] (4) A polymer of an .alpha.-olefin which is obtained in
accordance with a process described in any of (1) to (3) and has a
weight-average molecular weight in a range of 300 to 1,000,000;
[0017] (5) A polymer of an .alpha.-olefin which is obtained by
hydrogenating a polymer of an .alpha.-olefin described in any of
(4); and
[0018] (6) A lubricant which comprises a polymer of an
.alpha.-olefin described in any of (4) and (5).
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0019] The present invention relates to the process for producing a
polymer of an .alpha.-olefin and the lubricant which are described
above.
[0020] The present invention will be described in detail in the
following.
[0021] 1. The Process for Producing a Polymer of an
.alpha.-olefin
[0022] In accordance with the process of the present invention, an
.alpha.-olefin having at least 4 carbon atoms is polymerized in the
presence of a catalyst for producing polymers of olefins which
comprises:
[0023] (A) at least one compound selected from transition metal
compounds represented by following general formulae (I) and (II):
2
[0024] wherein R.sup.1 to R.sup.12 and X.sup.1 to X.sup.4 each
independently represent hydrogen atom, a halogen atom, a
hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group
having 1 to 20 carbon atoms and a halogen atom, a group having
silicon, a group having oxygen, a group having sulfur, a group
having nitrogen or a group having phosphorus; adjacent groups among
groups represented by R.sup.1 to R.sup.12 and X.sup.1 to X.sup.4
may form a ring by forming bonds between each other; three groups
represented by R.sup.9 may be the same with or different from each
other; three groups represented by R.sup.10 may be the same with or
different from each other; Y.sup.1 to Y.sup.4 each independently
represent a divalent group which forms a bond between two ligands
and is selected from hydrocarbon groups having 1 to 20 carbon
atoms, hydrocarbon groups having 1 to 20 carbon atom and a halogen
atom, a group having silicon, a group having germanium, a group
having tin, --O--, --CO--, --S--, --SO.sub.2--, --NR.sup.13--,
--PR.sup.13--, --P(O)R.sup.13--, --BR.sup.13-- and --AlR.sup.13--,
R.sup.13 representing hydrogen atom, a halogen atom, a hydrocarbon
group having 1 to 20 carbon atoms or a hydrocarbon group having 1
to 20 carbon atoms and a halogen atom, and M.sup.1 and M.sup.2 each
independently represent a transition metal of Groups 4 to 6 of the
Periodic Table; and
[0025] (B) at least one compound selected from (b-1) organoaluminum
oxy compounds and (b-2) ionic compounds which can be converted into
cations by reaction with the transition metal compounds of
component (A); and in the presence of hydrogen, where
necessary.
[0026] The compound represented by general formula (I) described
above may be a transition metal compound in which the groups
represented by Y.sup.1 and Y.sup.2 are each bonded to ligands in
the meso form or in the racemic form. It is preferable that the
groups represented by Y.sup.1 and Y.sup.2 are bonded to ligands in
the meso form.
[0027] Preferable examples of the compound represented by general
formula (I) described above include transition metal compounds of
Groups 4 to 6 of the Periodic Table which are represented by the
following general formulae (I)A and (I)B: 3
[0028] wherein R.sup.14 to R.sup.31, X.sup.1 and X.sup.2 each
independently represent hydrogen atom, a halogen atom, a
hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group
having 1 to 20 carbon atoms and a halogen atom, a group having
silicon, a group having oxygen, a group having sulfur, a group
having nitrogen or a group having phosphorus; adjacent groups among
groups represented by R.sup.14 to R.sup.31, X.sup.1 and X.sup.2 may
form a ring by forming bonds between each other; Y.sup.1 and
Y.sup.2 each independently represent a divalent group which forms a
bond between two ligands and is selected from hydrocarbon groups
having 1 to 20 carbon atoms, hydrocarbon groups having 1 to 20
carbon atom and a halogen atom, a group having silicon, a group
having germanium, a group having tin, --O--, --CO--, --S--,
--SO.sub.2--, --NR.sup.32--, --PR.sup.32--, --P(O)R.sup.32--,
--BR.sup.32-- and --AlR.sup.32--, R.sup.32 representing hydrogen
atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon
atoms or a hydrocarbon group having 1 to 20 carbon atoms and a
halogen atom, and M.sup.1 represents a transition metal of Groups 4
to 6 of the Periodic Table.
[0029] Specific examples of the compound represented by general
formula (I)A include dichloro compounds such as (1,1'-ethylene)
(2,2'-ethylene) Bisindenyl zirconium dichloride, (1,1'-ethylene)
(2,2'-ethylene)bis (3-methylindenyl)zirconium dichloride,
(1,1'-ethylene) (2,2'-ethylene)bis(4-methylindenyl)zirconium
dichloride, (1,1'-ethylene)
(2,2'-ethylene)bis(5-methylindenyl)zirconium dichloride,
(1,1'-ethylene) (2,2'-ethylene)bis(5,6-benzoindenyl)zirconium
dichloride, (1,1'-ethylene)
(2,2'-ethylene)bis(4,5-benzoindenyl)zirconium dichloride,
(1,1'-ethylene) (2,2'-ethylene)bis(5,6-dimethylindenyl)zirconium
dichloride, (1,1'-dimethylsilylene) (2,2'-dimethylsilylene)bis
indenyl zirconium dichloride, (1,1'-dimethylsilylene)
(2,2'-dimethylsilylene)bis(3-methylin- denyl)zirconium dichloride,
(1,1'-dimethylsilylene)
(2,2'-dimethylsilylene)bis(4-methylindenyl)zirconium dichloride,
(1,1'-dimethylsilylene)
(2,2'-dimethylsilylene)bis(5-methyl-indenyl)zirco- nium dichloride,
(1,1'-dimethylsilylene) (2,2'-dimethyl-silylene)bis(5,6-b-
enzoindenyl)zirconium dichloride, (1,1'-dimethylsilylene)
(2,2'-dimethylsilylene)bis(4,5-benzoindenyl)zirconium dichloride,
(1,1'-dimethylsilylene)
(2,2'-dimethylsilylene)bis(5,6-dimethylindenyl)zi- rconium
dichloride, (1,1'-dimethylsilylene) (2,2'-ethylene)bis indenyl
zirconium dichloride, (1,1'-dimethylsilylene)
(2,2'-ethylene)bis(3-methyl- indenyl)zirconium dichloride,
(1,1'-dimethylsilylene)
(2,2'-ethylene)bis(4-methylindenyl)zirconium dichloride,
(1,1'-dimethylsilylene)
(2,2'-ethylene)bis(5-methylindenyl)zirconium dichloride,
(1,1'-dimethylsilyene) (2,2'-ethylene)bis(5,6-benzoindenyl)zi-
rconium dichloride, (1,1'-dimethylsilylene)
(2,2'-ethylene)bis(4,5-benzoin- denyl)zirconium dichloride,
(1,1'-dimethylsilylene)
(2,2'-ethylene)bis(5,6-dimethylindenyl)zirconium dichloride,
(1,1'-ethylene) (2,2'-dimethylsilylene)bisindenyl zirconium
dichloride, (1,1'-ethylene)
(2,2'-dimethylsilylene)bis(3-methylindenyl)zirconium dichloride,
(1,1'-ethylene) (2,2'-dimethylsilylene)bis(4-methylindenyl)zi-
rconium dichloride, (1,1'-ethylene)
(2,2'-dimethyl-silylene)bis(5-methylin- denyl)zirconium dichloride,
(1,1'-ethylene) (2,2'-dimethylsilylene)bis(5,6-
-benzoindenyl)zirconium dichloride, (1,1'-ethylene)
(2,2'-dimethylsilylene)bis(4,5-benzoindenyl)zirconium dichloride,
(1,1'-ethylene)
(2,2'-dimethylsilylene)bis(5,6-dimethylindenyl)zirconium
dichloride, (1,1'-dimethylsilylene) (2,2'-isopropylidene)bis
indenyl zirconium dichloride, (1,1'-dimethylsilylene)
(2,2'-isopropylidene)bis(3-- methyl-indenyl)zirconium dichloride,
(1,1'-dimethylsilylene)
(2,2'-isopropylidene)bis(4-methylindenyl)zirconium dichloride,
(1,1'-dimethylsilylene)
(2,2'-isopropylidene)bis(5-methylindenyl)zirconiu- m dichloride,
(1,1'-dimethylsilylene) (2,2'-isopropylidene)bis(5,6-benzoin-
denyl)zirconium dichloride, (1,1'-dimethylsilylene)
(2,2'-isopropylidene)bis(4,5-benzo-indenyl)zirconium dichloride,
(1,1'-dimethylsilylene)
(2,2'-isopropylidene)bis(5,6-dimethylindenyl)zirc- onium
dichloride; dimethyl compounds, diethyl compounds, dihydro
compounds, diphenyl compounds and dibenzyl compounds corresponding
to the above dichloro compounds; titanium complex compounds
corresponding to the above compounds; and hafnium complex compounds
corresponding to the above compounds.
[0030] Specific examples of the compound represented by general
formula (I)B include dichloro compounds such as (1,1'-ethylene)
(2,2'-ethylene) indenyl (3,5-dimethylcyclopentadienyl)zirconium
dichloride, (1,1'-ethylene)
(2,2'-ethylene)indenyl(3,4-dimethylcyclopentadienyl)zirco- nium
dichloride, (1,1'-ethylene) (2,2'-ethylene)indenyl
(3-methyl-cyclopentadienyl)zirconium dichloride, (1,1'-ethylene)
(2,2'-ethylene) (4-methylindenyl)
(3,5-dimethylcyclopentadienyl)zirconium dichloride, (1,1'-ethylene)
(2,2'-ethylene) (4-methylindenyl)
(3-methylcyclopentadienyl)zirconium dichloride, (1,1'-ethylene)
(2,2'-ethylene) (5-methylindenyl)
(3,5-dimethylcyclopentadienyl)zirconium dichloride, (1,1'-ethylene)
(2,2'-ethylene) (5-methylindenyl)
(3-methylcyclopentadienyl)zirconium dichloride,
(1,1'-dimethylsilylene)
(2,2'-isopropylidene)indenyl(3,5-dimethylcyclopentadienyl)zirconium
dichloride, (1'-dimethylsilylene) (2,2'-isopropylidene)indenyl
(3,4-dimethylcyclopentadienyl)zirconium dichloride,
(1,1'-dimethylsilylene) (2,2'-isopropylidene)indenyl
(3-methyl-cyclopentadienyl)zirconium dichloride,
(1,1'-dimethylsilylene) (2,2'-isopropylidene) (4-methylindenyl)
(3,5-dimethylcyclopentadienyl)zir- conium dichloride,
(1,1'-dimethylsilylene) (2,2'-isopropylidene)(4-methyli- ndenyl)
(3-methylcyclopentadienyl)zirconium dichloride,
(1,1'-dimethylsilylene) (2,2'-isopropylidene) (5-methylindenyl)
(3,5-dimethylcyclopentadienyl)zirconium dichloride and
(1,1'-dimethylsilylene) (2,2'-isopropylidene) (5-methyl-indenyl)
(3-methylcyclopentadienyl)zirconium dichloride; and dimethyl
compounds, diethyl compounds, dihydro compounds, diphenyl compounds
and dibenzyl compounds corresponding to the above compounds of
transition metals of Group 4 of the Periodic Table.
[0031] Preferable examples of the compound represented by general
formula (II) described above include transition metal compounds of
Groups 4 to 6 of the Periodic Table represented by the following
general formulae (II)A and (II)B: 4
[0032] wherein R.sup.33 to R.sup.54, X.sup.3 and X.sup.4 each
independently represent hydrogen atom, a halogen atom, a
hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group
having 1 to 20 carbon atoms and a halogen atom, a group having
silicon, a group having oxygen, a group having sulfur, a group
having nitrogen or a group having phosphorus; adjacent groups among
groups represented by R.sup.33 to R.sup.54, X.sup.3 and X.sup.4 may
form a ring by forming bonds between each other; Y.sup.3 and
Y.sup.4 each independently represent a divalent group which forms a
bond between two ligands and is selected from hydrocarbon groups
having 1 to 20 carbon atoms, hydrocarbon groups having 1 to 20
carbon atom and a halogen atom, a group having silicon, a group
having germanium, a group having tin, --O--, --CO--, --S--,
--SO.sub.2--, --NR.sup.55--, --PR.sup.55--, --P(O)R.sup.55--,
--BR.sup.55-- and --AlR.sup.55--, R.sup.55 representing hydrogen
atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon
atoms or a hydrocarbon group having 1 to 20 carbon atoms and a
halogen atom, and M.sup.2 represents a transition metal of Groups 4
to 6 of the Periodic Table.
[0033] Specific examples of the compound represented by general
formula (II)A include dichloro compounds such as (1,1'-ethylene)
(7,7'-ethylene)bisindenylzirconium dicloride, (1,1'-ethylene)
(7,7'-ethylene)bis(2-methylindenyl)zirconium dichloride,
(1,1'-ethylene) (7,7'-ethylene)bis(3-methylindenyl)zirconium
dichloride, (1,1'-dimethylsilylene)
(7,7'-dimethylsilylene)bisindenylzirconium dichloride,
(1,1'-dimethylsilylene) (7,7'-dimethylsilylene)bis(2-methylin-
denyl)zirconium dichloride, (1,1,-dimethylsilylene)
(7,7'-dimethylsilylene)bis(3-methylindenyl)zirconium dichloride,
(1,1'-ethylene) (7,7'-dimethylsilylene)bisindenylzirconium
dichloride, (1,1'-ethylene)
(7,7'-dimethylsilylene)bis(2-methylindenyl)-zirconium dichloride,
(1,1'-ethylene) (7,7'-dimethylsilylene)bis(3-methylindenyl)zi-
rconium dichloride, (1,1'-dimethylsilylene)
(7,7'-ethylene)bisindenylzirco- nium dichloride,
(1,1'-dimethylsilylene) (7,7'-ethylene)bis(2-methylindeny- l)
zirconium dichloride and (1,1'-dimethyl-silylene)
(7,7'-ethylene)bis(3-methylindenyl)zirconium dichloride; and
dimethyl compounds, diethyl compounds, dihydro compounds, diphenyl
compounds and dibenzyl compounds corresponding to the above
compounds of transition metals of Group 4 of the Periodic
Table.
[0034] Specific examples of the compound represented by general
formula (II)B include dichloro compounds such as (1,1'-ethylene)
(2,7'-ethylene) (fluorenyl) (indenyl)zirconium dichloride,
(1,1'-ethylene) (2,7'-ethylene) (fluorenyl)
(2-methylindenyl)zirconium dichloride,
(1,1'-ethylene)-(2,7'-ethylene) (fluorenyl)
(3-methylindenyl)zirconium dichloride, (1,1'-ethylene)
(2,7'-ethylene) (fluorenyl) (6-methylindenyl)zirconium dichloride,
(1,1'-ethylene) (2,7'-ethylene) (9-methylfluorenyl)
(indenyl)zirconium dichloride, (1,1'-ethylene) (2,7'-ethylene)
(8-methylfluorenyl) (indenyl)zirconium dichloride,
(1,1'-dimethylsilylene) (2,7'-ethylene) (fluorenyl)
(indenyl)zirconium dichloride, (1,1'-dimethylsilylene)
(2,7'-ethylene) (fluorenyl) (2-methylindenyl)zirconium dichloride,
(1,1'-dimethyl-silylene) (2,7'-ethylene) (fluorenyl)
(3-methylindenyl)zirconium dichloride, (1,1'-dimethylsilylene)
(2,7'-ethylene) (fluorenyl) (6-methylindenyl)zirconium dichloride,
(1,1'-dimethylsilylene) (2,7'-ethylene) (9-methyl-fluorenyl)
(indenyl)zirconium dichloride, (1,1'-dimethylsilylene)
(2,7'-ethylene) (8-methylfluorenyl) (indenyl)zirconium dichloride,
(1,1'-ethylene) (2,7'-dimethylsilylene) (fluorenyl)
(indenyl)zirconium dichloride, (1,1'-ethylene)
(2,7'-dimethylsilylene) (fluorenyl) (2-methylindenyl)zirconium
dichloride, (1,1'-ethylene) (2,7'-dimethylsilylene) (fluorenyl)
(3-methyl-indenyl)zirconium dichloride, (1,1'-ethylene)
(2,7'-dimethylsilylene) (fluorenyl) (6-methylindenyl)zirconium
dichloride, (1,1'-ethylene) (2,7'-dimethylsilylene)
(9-methylfluorenyl) (indenyl)zirconium dichloride, (1,1'-ethylene)
(2,7-dimethylsilylene) (8-methylfluorenyl) (indenyl)zirconium
dichloride, (1,1'-dimethylsilylene) (2,7'-dimethylsilylene)
(fluorenyl) (indenyl)zirconium dichloride, (1,1'-dimethylsilylene)
(2,7'-dimethylsilylene) (fluorenyl) (2-methylindenyl)zirconium
dichloride, (1,1'-dimethylsilylene) (2,7'-dimethylsilylene)
(fluorenyl) (3-methylindenyl)zirconium dichloride,
(1,1'-dimethylsilylene) (2,7'-dimethylsilylene) (fluorenyl)
(6-methylindenyl)zirconium dichloride, (1,1'-dimethylsilylene)
(2,7'-dimethylsilylene) (9-methylfluorenyl) (indenyl)zirconium
dichloride and (1,1'-dimethylsilylene) (2,7'-dimethylsilylene)
(8-methylfluorenyl) (indenyl)zirconium dichloride; and dimethyl
compounds, diethyl compounds, dihydro compounds, diphenyl compounds
and dibenzyl compounds corresponding to the above compounds of
transition metals of Group 4 of the Periodic Table.
[0035] The transition metal compounds used as component (A) may be
used singly or in combination of two or more.
[0036] Examples of the organoaluminum oxy compound of component
(b-1) of component (B) include chain aluminoxanes represented by
the following general formula (III): 5
[0037] wherein R.sup.56 represents a hydrocarbon group such as an
alkyl group having 1 to 20 carbon atoms and preferably having 1 to
12 carbon atoms, an alkenyl group, an aryl group and an arylalkyl
group or a halogen atom; n represents the degree of polymerization
which is an integer, in general, in the range of 2 to 50 and
preferably in the range of 2 to 40; and the groups and the atoms
represented by a plurality of R.sup.56 may the same with or
different from each other; and cyclic aluminoxanes represented by
the following general formula (IV): 6
[0038] wherein R.sup.56 and n are as defined above. Specific
examples of the above compounds include methylaluminoxane,
ethylaluminoxane and isobutylaluminoxane.
[0039] As the process for producing the above aluminoxane, a
process in which an alkylaluminum is brought into contact with a
condensation agent such as water can be conducted. However, the
process is not particularly limited and any conventional process
can be conducted. Examples of the process include (i) a process in
which an organoaluminum compound is dissolved in an organic solvent
and the solution is brought into contact with water, (ii) a process
in which an organoaluminum compound is added into the mixture for
polymerization in advance and water is added to the mixture
thereafter, (iii) a process in which crystal water contained in a
salt of a metal or water adsorbed to an inorganic substance or an
organic substance is brought into reaction with an organoaluminum
compound and (iv) a process in which a tetraalkyldialuminoxane is
reacted with a trialkylaluminum and the product is further reacted
with water. An aluminoxane insoluble in toluene may be used. The
aluminoxane may be used singly or in combination of two or
more.
[0040] As component (b-2), any ionic compound can be used as long
as the ionic compound can be converted into a cation by reaction
with the transition metal compound of component (A). Preferable
examples of the above compound include compounds represented by the
following general formulae (V) and (VI):
([L.sup.1-R.sup.57].sup.k+).sub.a([Z].sup.-).sub.b (V)
([L.sup.2].sup.k+).sub.a([Z].sup.-).sub.b (VI)
[0041] In general formulae (V) and (VI), L.sup.2 represents
M.sup.5, R.sup.58R.sup.59M.sup.6, R.sup.60.sub.3C or
R.sup.61M.sup.6, L.sup.1 represents a Lewis base and [Z].sup.-
represents an anion which does not coordinate and includes anions
represented by [Z.sup.1].sup.- and [Z.sup.2].sup.-. [Z.sup.1].sup.-
represents an anion in which a plurality of groups are bonded to an
element. [Z.sup.1].sup.- is also expressed as
[M.sup.7G.sup.1G.sup.2 . . . G.sup.f].sup.-, wherein M.sup.7
represents an element of Groups 5 to 15 of the Periodic Table and
preferably an element of Groups 13 to 15 of the Periodic Table,
G.sup.1 to G.sup.f each represent hydrogen atom, a halogen atom, an
alkyl group having 1 to 20 carbon atoms, a dialkylamino group
having 2 to 40 carbon atoms, an alkoxy group having 1 to 20 carbon
atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group
having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40
carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, a
hydrocarbon group having 1 to 20 carbon atoms and substituted with
a halogen atom, an acyloxy group having 1 to 20 carbon atoms, an
organometalloid group or a hydrocarbon group having 2 to 20 carbon
atoms and a hetero atom. Two or more groups among the groups
represented by G.sup.1 to G.sup.f may form a ring. f represents an
integer of [the valency of the central metal atom M.sup.7]+1.
[Z.sup.2].sup.- represents an anion which is a Br.phi.nsted acid
alone, a conjugate base as a combination of the Br.phi.nsted acid
and a Lewis acid or a conjugate base of an acid defined, in
general, as a superstrong acid and has a logarithm of the inverse
of the acid dissociation constant (pKa) of -10 or smaller. A Lewis
base may be coordinated. R.sup.57 represents hydrogen atom, an
alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to
20 carbon atoms, an alkylaryl group or an arylalkyl group. R.sup.58
and R.sup.59 each represent cyclopentadienyl group, a substituted
cyclopentadienyl group, indenyl group or fluorenyl group. R.sup.60
represents an alkyl group having 1 to 20 carbon atoms, an aryl
group, an alkylaryl group or an arylalkyl group. R.sup.61
represents a ligand having a large ring such as
tetraphenylporphyrin and phthalocyanine. k represents an integer of
1 to 3 which is the ionic charge number of [L.sup.1--R.sup.57] or
[L.sup.2], a represents an integer of 1 or greater and
b=(k.times.a). M.sup.5 represents an element including an element
of Groups 1 to 3, 11 to 13 and 17 of the Periodic Table and MG
represents an element of Groups 7 to 12 of the Periodic Table.
[0042] Examples of the Lewis base group represented by L.sup.1
include ammonia; amines such as methylamine, aniline,
dimethylamine, diethylamine, N-methylaniline, diphenylamine,
N,N-dimethylaniline, trimethylamine, triethylamine,
tri-n-butylamine, methyldiphenylamine, pyridine,
p-bromo-N,N-dimethylaniline and p-nitro-N,N-dimethylaniline;
phosphines such as triethylphosphine, triphenylphosphine and
diphenylpliosphine; thioethers such as tetrahydrothiophene; esters
such as ethyl benzoate; and nitriles such as acetonitrile and
benzonitrile.
[0043] Examples of the atom and the groups represented by R.sup.57
include hydrogen atom, methyl group, ethyl group, benzyl group and
trityl group. Examples of the groups represented by R.sup.58 and
R.sup.59 include cyclopentadienyl group, methylcyclopentadienyl
group, ethyl-cyclopentadienyl group and pentamethylcyclopentadienyl
group. Examples of the group represented by R.sup.60 include phenyl
group, p-tolyl group and p-methoxyphenyl group. Examples of the
ligand represented by R.sup.61 include tetraphenylporphyrin,
phthalocyanine, allyl group and methallyl group. Examples of the
element represented by M.sup.5 include Li, Na, K, Ag, Cu, Br, I and
I.sub.3. Examples of the element represented by M.sup.6 include Mn,
Fe, Co, Ni and Zn.
[0044] In the anion represented by [Z.sup.1].sup.-, which is also
expressed as [M.sup.7G.sup.1G.sup.2 . . . G.sup.f].sup.-, examples
of the element represented by M.sup.7 include B, Al, Si, P, As and
Sb. Among these elements, B and Al are preferable. Examples of the
atoms and groups represented by G.sup.1 to G.sup.f include
dialkylamino groups such as dimethylamino group and diethylamino
group; alkoxy groups and aryloxy groups such as methoxy group,
ethoxy group, n-propoxy group and phenoxy group; hydrocarbon groups
such as methyl group, ethyl group, n-propyl group, isopropyl group,
n-butyl group, isobutyl group, n-octyl group, n-eicosyl group,
phenyl group, p-tolyl group, benzyl group, 4-t-butylphenyl group
and 3,5-dimethylphenyl group; halogen atoms such as fluorine atom,
chlorine atom, bromine atom and iodine atom; hydrocarbon groups
having a heteroatom such as p-fluorophenyl group,
3,5-difluorophenyl group, pentachlorophenyl group,
3,4,5-trifluorophenyl group, pentafluorophenyl group,
3,5-bis(trifluoromethyl)phenyl group and bis(trimethylsilyl)methyl
group; and organometalloid groups such as pentamethylantimony
group, trimethylsilyl group, trimethylgermyl group, diphenylarsine
group, dicyclohexylantimony group and diphenylboron group.
[0045] Examples of the anion which is represented by
[Z.sup.2].sup.-, does not coordinate and has a logarithm of the
inverse of the acid dissociation constant (pKa) of -10 or smaller,
i.e., the Br.phi.nsted acid alone or the conjugate base as a
combination of the Br.phi.nsted acid and a Lewis acid, include
trifluoromethanesulfonate anion (CF.sub.3SO.sub.3).sup.-,
bis(trifluoromethane-sulfonyl)methyl anion,
bis(trifluoromethanesulfonyl)benzyl anion,
bis(trifluoromethanesulfonyl)a- mide, perchlorate anion
(ClO.sub.4).sup.-, trifluoroacetate anion (CF.sub.3COO).sup.-,
hexafluoroantimony anion (SbF.sub.6).sup.-, fluorosulfonate anion
(FSO.sub.3).sup.-, chlorosulfonate anion (ClSO.sub.3).sup.-,
fluorosulfate anion/antimony pentafluoride
(FSO.sub.3/SbF.sub.5).sup.-, fluorosulfonate anion/arsenic
pentafluoride (FSO.sub.3/AsF.sub.5).sup.- and
trifluoromethanesulfonate anion/antimony pentafluoride
(CF.sub.3SO.sub.3/SbF.sub.5).sup.-.
[0046] Examples of the compound of component (b-2) include
triethylammonium tetraphenyl borate, tri-n-butylammonium
tetraphenyl borate, trimethylammonium tetraphenyl borate,
teraethylammonium tetraphenyl borate, methyl(tri-n-butyl)ammonium
tetraphenyl borate, benzyl(tri-n-butyl)ammonium tetraphenyl borate,
dimethyldiphenyl-ammonium tetraphenyl borate,
triphenyl(methyl)ammonium tetraphenyl borate, trimethylanilinium
tetraphenyl borate, methylpyridinium tetraphenyl borate,
benzylpyridinium tetraphenyl borate, methyl
(2-cyanopyridinium)tetraphenyl borate, triethylammonium
tetrakis(pentafluorophenyl)borate, tri-n-butylammonium
tetrakis(pentafluorophenyl)borate, tripentylammonium
tetrakis(pentafluorophenyl)borate, tetra-n-butylammonium
tetrakis(pentafluorophenyl)borate, tetraethylammonium
tetrakis(pentafluorophenyl)borate, benzyl(tri-n-butyl)ammonium
tetrakis(pentafluorophenyl)borate, methyldiphenylammonium
tetrakis(pentafluorophenyl)borate, triphenyl(methyl)ammonium
tetrakis(pentatluorophenyl)borate, methylanilinium
tetrakis(pentafluorophenyl)borate, dimethylanilinium
tetrakis(pentafluorophenyl)borate, trimethylanilinium
tetrakis(pentafluorophenyl)borate, methylpyridinium
tetrakis(pentafluorophenyl)borate, benzylpyridinium
tetrakis(pentafluorophenyl)borate,
methyl(2-cyanopyridinium)tetrakis(pent- afluorophenyl)borate,
benzyl(2-cyanopyridinium)tetrakis(pentafluorophenyl)- borate,
methyl(4-cyanopyridinium)tetrakis(pentafluorophenyl)borate,
triphenylphosphonium tetrakis(pentafluorophenyl)borate,
dimethylanilinium tetrakis[bis(3,5-ditrifluoromethyl)phenyl]borate,
ferrocenium tetraphenyl borate, silver tetraphenyl borate, trityl
tetraphenyl borate, tetraphenylporphyrin manganese tetraphenyl
borate, ferrocenium tetrakis(pentafluorophenyl)borate,
(1,1'-dimethylferrocenium)tetrakis(pen- tafluorophenyl)borate,
decamethylferrocenium tetrakis(pentafluorophenyl)bo- rate, silver
tetrakis (pentafluorophenyl)borate, trityl
tetrakis(pentafluorophenyl)borate, lithium
tetrakis(pentafluorophenyl)bor- ate, sodium
tetrakis(pentafluorophenyl)borate, tetraphenylporphyrin manganese
tetrakis(pentafluorophenyl)borate, silver tetrafluoroborate, silver
hexafluorophosphate, silver hexafluoroarsenate, silver perchlorate,
silver trifluoroacetate and silver trifluoromethanesulfonate- .
[0047] The compounds of component (b-2) may be used singly or in
combination of two or more.
[0048] The relative amounts of component (A) and component (B) used
in the present invention are as follows: when component (b-1) is
used as component (B), the ratio of the amounts by mole of
component (A) to component (B) is preferably 1:1 to 1:1,000,000 and
more preferably 1:10 to 10,000 and, when component (b-2) is used as
component (B), the ratio of the amounts by mole of component (A) to
component (B) is preferably 10:1 to 1:100 and more preferably 2:1
to 1:10. As component (B), any of component (b-1) and component
(b-2) may be used singly or in combination of two or more.
[0049] The catalyst for producing a polymer of an .alpha.-olefin
used in the present invention may comprise component (A) and
component (B) described above as the main components or component
(A), component (B) and (C) an organoaluminum compound as the main
components. As the organoaluminum compound of component (C), a
compound represented by general formula (VII) is used.
R.sup.62.sub.vAlQ.sub.3-v (VII)
[0050] In general formula (VII), R.sup.62 represents an alkyl group
having 1 to 10 carbon atoms, Q represents hydrogen atom, an alkoxy
group having 1 to 20 carbon atoms, an aryl group having 6 to 20
carbon atoms or a halogen atom and v represents an integer of 1 to
3.
[0051] Examples of the compound represented by general formula
(VII) include trimethylaluminum, triethylaluminum,
triisopropylaluminum, triisobutylaluminum, dimethylaluminum
chloride, diethylaluminum chloride, methylaluminum dichloride,
ethylaluminum dichloride, dimethylaluminum fluoride,
diisobutylaluminum hydride, diethylaluminum hydride and
ethylaluminum sesquichloride. The organoaluminum compound may be
used singly or in combination of two or more. Component (C) is used
in such an amount that the ratio of the amounts by mole of
component (A) to component (C) is preferably 1:1 to 1:10,000 and
more preferably 1:5 to 1:2,000 and most preferably 1:10 to 1:1,000.
By using component (C), the polymerization activity based on the
amount of the transition metal can be increased. However, when the
amount of component (C) exceeds the above range, a portion of the
organoaluminum compound is not utilized and residues of the
organoaluminum compound remains in the polymer in a great amount.
Therefore, such an amount is not preferable.
[0052] In the present invention, at least one of the components of
the catalyst may be supported on a suitable support. The type of
the support is not particularly limited. A support of an inorganic
oxide, an inorganic support other than oxides or an organic support
may be used. From the standpoint of controlling morphology, a
support of an inorganic oxide or an inorganic support other than
oxides is preferable.
[0053] Examples of the support of an inorganic oxide include
SiO.sub.2, Al.sub.2O.sub.3, MgO, ZrO.sub.2, TiO.sub.2,
Fe.sub.2O.sub.3, B.sub.2O.sub.3, CaO, ZnO, BaO, ThO.sub.2 and
mixtures of these compounds and, more specifically, silica-alumina,
zeolite, ferrite and glass fiber. Among these substances, SiO.sub.2
and Al.sub.2O.sub.3 are preferable. The above inorganic support may
contain small amounts of carbonates, nitrates and sulfates.
Examples of the inorganic support other than oxides include
magnesium compounds represented by MgR.sup.63.sub.xX.sup.5.sub.y
such as MgCl.sub.2 and Mg(OC.sub.2H.sub.5).sub.2 and complexes of
the magnesium compounds. In the formula, R.sup.63 represents an
alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1
to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms,
X.sup.5 represents a halogen atom or an alkyl group having 1 to 20
carbon atoms, x represents a number of 0 to 2, y represents a
number of 0 to 2 and x+y=2. A plurality of groups represented by
R.sup.63 may be the same with or different from each other and a
plurality of groups and atoms represented by X.sup.5 may be the
same with or different from each other.
[0054] Examples of the organic support include polymers such as
polystyrene, copolymers of styrene and divinylbenzene,
polyethylene, polypropylene, substituted polystyrenes and
polyarylates, starch and carbon black. As the support used in the
present invention, MgCl.sub.2, MgCl(OC.sub.2H.sub.5),
Mg(OC.sub.2H.sub.5).sub.2, SiO.sub.2 and Al.sub.2O.sub.3 are
preferable. The properties of the support are different depending
on the type and the process of preparation. The average particle
diameter is, in general, 1 to 300 .mu.m, preferably 10 to 200 .mu.m
and more preferably 20 to 100 .mu.m. When the average particle
diameter is smaller than the above range, the amount of fine powder
in the polymer increases. When the average particle diameter
exceeds the above range, the amount of rough particles in the
polymer increases and a decrease in the bulk density and clogging
of a hopper may take place. The specific surface area of the
support is, in general, 1 to 1,000 m.sup.2/g and preferably 50 to
500 m.sup.2/g. The volume of pores is, in general, 0.1 to 5
cm.sup.3/g and preferably 0.3 to 3 cm.sup.3/g. When any of the
specific surface area and the volume of pores is outside the above
ranges, the catalyst activity occasionally decreases. The specific
surface area and the volume of pores can be obtained, for example,
from the volume of adsorbed nitrogen gas in accordance with the BET
method (J. Am. Chem. Soc., 60, 309 (1983)). It is preferable that
the above support is used after being calcined, in general, at 150
to 1,000.degree. C. and preferably at 200 to 800.degree. C.
[0055] When the catalyst component is supported on the support
described above, it is preferable that at least one of components
(A) and (B) is supported and it is more preferable that components
(A) and (B) are both supported. The process for supporting at least
one of components (A) and (B) is not particularly limited. Examples
of the process include (i) a process in which at least one of
components (A) and (B) is mixed with a support; (ii) a process in
which a support is treated with an organoaluminum compound or a
silicon compound having a halogen and then at least one of
components (A) and (B) is mixed with the treated support in an
inert solvent; (iii) a process in which a support, at least one of
components (A) and (B) and an organoaluminum compound or a silicon
compound having a halogen are reacted; (iv) a process in which
component (A) or component (B) is supported on a support and then
mixed with component (B) or component (A), respectively; (v) a
process in which a product of a catalytic reaction of components
(A) and (B) is mixed with a support; and (vi) a process in which a
catalytic reaction of components (A) and (B) is conducted in the
presence of a support. In the reactions described above, an
organoaluminum compound of component (C) may be added.
[0056] The catalyst obtained as described above may be used for the
polymerization without further treatments or may be taken out as a
solid product after the solvent is removed and used for the
polymerization. In the present invention, the operation for
supporting at least one of components (A) and (B) on a support may
be conducted in the polymerization system so that the
polymerization catalyst is formed. For example, at least one of
components (A) and (B), a support and an organoaluminum compound of
component (C), where necessary, are placed into the polymerization
system and particles of the catalyst are formed by a preliminary
polymerization conducted by passing an olefin such as ethylene at
an ordinary pressure to 2 MPa at 20 to 200.degree. C. for 1 minute
to 2 hours.
[0057] In the present invention, it is preferable that component
(A) and the support described above are used in amounts such that
the ratio of the amounts by weight is 1:0.5 to 1:1,000 and more
preferably 1:1 to 1:50. It is preferable that component (B) and the
support are used in amounts such that the ratio of the amounts by
weight is 1:5 to 1:10,000 and more preferably 1:10 to 1:500. When a
mixture of two or more types of components are used as component
(B), it is preferable that the relative amounts by mass of each
component of component (B) and the support is in the above range.
It is preferable that component (A) and the support described above
are used in amounts such that the ratio of the amounts by weight is
1:5 to 1:10,000 and more preferably 1:10 to 1:500. When the
relative amounts of component (B) (either component (A) or
component (B)) and the support or the relative amounts of component
(A) and the support are outside the above range, the activity
occasionally decreases. The polymerization catalyst of the present
invention prepared as described above has an average particle
diameter, in general, in the range of 2 to 200 .mu.m, preferably in
the range of 10 to 150 .mu.m and more preferably in the range of 20
to 100 .mu.m; a specific surface area, in general, in the range of
20 to 1,000 m.sup.2/g and preferably in the range of 50 to 500
m.sup.2/g. When the average particle diameter is smaller than 2
.mu.m, the amount of fine particles in the polymer occasionally
increases. When the average particle diameter exceeds 200 .mu.m,
the amount of rough particles in the polymer occasionally
increases. When the specific surface area is smaller than 20
m.sup.2/g, the activity occasionally decreases. When the specific
surface area exceeds 1,000 m.sup.2/g, the bulk density of the
polymer occasionally decreases. In the present invention, it is
preferable that the amount of the transition metal per 100 g of the
support is, in general, in the range of 0.05 to 10 g and preferably
in the range of 0.1 to 2 g. When the amount of the transition metal
is outside the above range, the activity occasionally decreases. An
industrially advantageous process can be obtained by supporting the
catalyst as described above.
[0058] As the .alpha.-olefin having 4 or more carbon atoms used in
the present invention, an .alpha.-olefin having 4 to 20 carbon
atoms is preferable. Examples of the .alpha.-olefin include
1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene,
1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene,
1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene,
1-octadecene, 1-nonadecene and 1-eicocene. The .alpha.-olefin may
be used singly or in combination of two or more. Among the above
.alpha.-olefins, .alpha.-olefins having 4 to 14 carbon atoms are
preferable and .alpha.-olefins having 6 to 10 carbon atoms which
are easily available and have low prices are more preferable.
[0059] In the present invention, the process for polymerization is
not particularly limited. Any of the slurry polymerization, the gas
phase polymerization, the bulk polymerization, the solution
polymerization and the suspension polymerization may be used. As
for the conditions of polymerization, the temperature of
polymerization is, in general, in the range of -100 to 250.degree.
C., preferably in the range of -50 to 200.degree. C. and more
preferably in the range of 0 to 160.degree. C. As for the amount of
the catalyst relative to the amount of the raw material of the
reaction, it is preferable that the ratio of the amounts by mole of
the monomer of the raw material to component (A) is in the range of
1 to 10.sup.8 and more preferably in the range of 100 to 10.sup.5.
The time of polymerization is, in general, in the range of 5
minutes to 10 hours. The pressure of polymerization is preferably
in the range of an ordinary pressure to 20 MPa and more preferably
in the range of an ordinary pressure to 10 MPa.
[0060] In the process of the present invention, it is preferable
that hydrogen is added in the polymerization of an .alpha.-olefin
having 4 or more carbon atoms since the polymerization activity is
enhanced. When hydrogen is added, the pressure of hydrogen is, in
general, in the range of an ordinary pressure to 5 MPa, preferably
in the range of an ordinary pressure to 3 MPa and more preferably
in the range of an ordinary pressure to 2 MPa. When a solvent is
used for the polymerization, an aromatic hydrocarbon such as
benzene, toluene, xylene and ethylbenzene, an alicyclic hydrocarbon
such as cyclopentane, cyclohexane and methylcyclohexane, an
aliphatic hydrocarbon such as pentane, hexane, heptane and octane
or a halogenated hydrocarbon such as chloroform and dichloromethane
can be used as the solvent. The solvent may be used singly or in
combination of two or more. A monomer such as 1-butene may be used
as the solvent. The polymerization may be conducted without using
any solvents depending on the process of the polymerization.
[0061] In the present invention, a preliminary polymerization may
be conducted using the above polymerization catalyst. The
preliminary polymerization can be conducted, for example, by
bringing a small amount of an olefin into contact with a solid
component of the catalyst. The process of the preliminary
polymerization is not particularly limited and a conventional
process can be used. The olefin used for the preliminary
polymerization is not particularly limited. For example, ethylene,
an .alpha.-olefin having 3 to 20 carbon atoms or a mixture of these
olefins may be used. It is advantageous that the same olefin as the
monomer used for the polymerization is used. The temperature of the
preliminary polymerization is, in general, in the range of -20 to
200.degree. C., preferably in the range of -10 to 130.degree. C.
and more preferably in the range of 0 to 80.degree. C. In the
preliminary polymerization, inert hydrocarbons, aliphatic
hydrocarbons, aromatic hydrocarbons and monomers may be used as the
solvent. Among these solvents, aliphatic hydrocarbons are
preferable. The preliminary polymerization may be conducted without
any solvents. In the preliminary polymerization, it is preferable
that the condition of the polymerization is adjusted so that the
product of the preliminary polymerization has an intrinsic
viscosity [.eta.] (as measured in decaline at 135.degree. C.) of
0.1 dl/g or greater and the amount of the product of the
preliminary polymerization is in the range of 1 to 10,000 g and
more preferably in the range of 10 to 1,000 g per 1 mmole of the
transition metal component of the catalyst. The copolymer of an
.alpha.-olefin of the present invention can be obtained efficiently
in accordance with the process described above.
[0062] The molecular weight of the polymer can be adjusted by
suitably selecting the type and the amount of the catalyst
components and the temperature of polymerization. The molecular
weight can also be adjusted by conducting the polymerization in the
presence of hydrogen. An inert gas such as nitrogen gas may be
present during the polymerization.
[0063] 2. The Polymer of an .alpha.-olefin
[0064] The polymer of an .alpha.-olefin is obtained in accordance
with the process for producing a polymer of an .alpha.-olefin
described above.
[0065] It is preferable that the polymer of an .alpha.-olefin of
the present invention has a weight-average molecular weight in the
range of 300 to 1,000,000 as measured in accordance with the gel
permeation chromatography. When the weight-average molecular weight
is smaller than 300, the molecular weight is so low that the effect
as a component of lubricant is occasionally not obtained. When the
molecular weight exceeds 1,000,000, the molecular weight is so high
that the effect as a component of lubricant is occasionally not
obtained. From the standpoint of the above effect, it is more
preferable that the molecular weight is in the range of 300 to
500,000. The method of obtaining the molecular weight in accordance
with the gel permeation chromatography will be described in detail
in EXAMPLES.
[0066] It is preferable that the polymer of an .alpha.-olefin of
the present invention has an intrinsic viscosity [.eta.] in the
range of 0.01 to 20 dl/g as measured in decaline at 135.degree. C.
When [.eta.] is smaller than 0.01 dl/g, the intrinsic viscosity is
so low that the effect as a component of lubricant is occasionally
not obtained. When [.eta.] exceeds 20 dl/g, the intrinsic viscosity
is so high that the effect as a component of lubricant is
occasionally not obtained. From the standpoint of the above effect,
it is more preferable that the intrinsic viscosity is in the range
of 0.1 to 10 dl/g and most preferably in the range of 0.1 to 5
dl/g.
[0067] It is preferable that the polymer of an .alpha.-olefin of
the present invention has a ratio (Mw/Mn) of the weight-average
molecular weight (Mw) to the number average molecular weight (Mn),
as measured in accordance with the gel permeation chromatography,
satisfying the following relation:
1<Mw/Mn.ltoreq.4
[0068] more preferably, the following relation:
1<Mw/Mn.ltoreq.3.5
[0069] and most preferably, the following relation:
1<Mw/Mn.ltoreq.3
[0070] The polymer of an .alpha.-olefin of the present invention
may be hydrogenated. When the polymer of an .alpha.-olefin is used
as lubricant, a hydrogenated polymer of an .alpha.-olefin obtained
from the above polymer of an .alpha.-olefin is preferable. The
process for hydrogenation is not particularly limited and a process
suitably selected from conventional processes can be used.
[0071] 3. The Lubricant
[0072] The lubricant of the present invention comprises at least
one of the polymer of an .alpha.-olefin and the hydrogenated
polymer of an .alpha.-olefin obtained from the polymer of an
.alpha.-olefin. The lubricant of the present invention comprises at
least one of the polymer of an .alpha.-olefin and the hydrogenated
polymer of an .alpha.-olefin obtained from the polymer of an
.alpha.-olefin in an amount of 0.01 to 100% by weight. The form of
application of the lubricant of the present invention is not
particularly limited. At least one of the polymer of an
.alpha.-olefin and the hydrogenated polymer of an .alpha.-olefin
obtained from the polymer of an .alpha.-olefin may be used as the
base oil. As the base oil, polymers having a wide range of
molecular weight can be used. When a polymer having a relatively
low molecular weight (a weight-average molecular weight in the
range of 300 to 3,000) is used as the base oil, the polymer may be
used singly or as a mixture with other base oils. The content of
the polymer in the base oil is not particularly limited. In
general, the content is in the range of 1 to 100% by weight.
[0073] As an example of other forms of application of the
lubricant, at least one of the polymer of an .alpha.-olefin and the
hydrogenated polymer of an .alpha.-olefin obtained from the polymer
of an .alpha.-olefin is used as an additive to lubricant. For
example, the polymer is added to lubricant as the viscosity index
improver. In this case, it is preferable that a polymer of an
.alpha.-olefin having a relatively high molecular weight is used.
For example, as the polymer of .alpha.-olefin having a high
molecular weight, a polymer having a weight-average molecular
weight which exceeds 3,000 and is 200,000 or smaller is used. The
amount of the polymer added to the lubricant is, in general, in the
range of 0.01 to 50% by weight.
[0074] The lubricant of the present invention may further comprise
various suitable conventional additives as long as the object of
the present invention is not adversely affected. Examples of the
additive include extreme pressure agents containing phosphorus such
as phosphoric acid esters and phosphorous acid esters; oiliness
improvers such as carboxylic acids such as oleic acid, stearic acid
and dimer acid and esters of carboxylic acids; antiwear agents such
as zinc dithiophosphate (ZnDTP, excluding allyl-type compounds),
zinc dithiocarbamate (ZnDTC), molybdenum oxysulfide dithiocarbamate
(MoDTC), nickel dithiophosphate (NiDTP) and nickel dithiocarbamate
(NiDTC); antioxidants such as amine antioxidants and phenol
antioxidants; metal inactivators such as thiadiazole and
benzotriazole; sludge dispersants such as alkenylsuccinic acids and
esters and imides of alkenylsuccinic acids; rust preventives such
as sorbitan esters and sulfonates, phenates and salicylates of
neutral alkaline earth metals; and defoaming agents such as
dimethylpolysiloxane and polyacrylates.
[0075] The type of the lubricant of the present invention is not
particularly limited. Examples of the lubricant include gasoline
engine oil (for 2-cycle and 4 cycle engines), oil for internal
combustion engines such as Diesel engine oil, gear oil, ATF, PSF,
oil for driving systems and chassis such as shock absorber oil,
turbine oil, hydraulic oil, transmission oil, machine oil, oil for
apparatuses such as refrigerating oil, oil for machine working such
as rolling oil, cutting oil and heat treatment oil, and grease.
[0076] To summarize the advantages of the present invention, the
polymer of an .alpha.-olefin which is useful as a component of
lubricant is efficiently obtained.
EXAMPLES
[0077] The present invention will be described more specifically
with reference to examples in the following. However, the present
invention is not limited to the examples. Physical properties of a
polymer of an .alpha.-olefin and a hydrogenated polymer obtained
from a polymer of an .alpha.-olefin were evaluated in accordance
with the following methods.
[0078] (1) Mw/Mn
[0079] Mw/Mn was measured using an apparatus manufactured by NIPPON
BUNKO Co., Ltd., GPC-880 (the column: TSKGMH-6.times.1 manufactured
by TOSO Co., Ltd. and GL-A120.times.1 and GL-A130.times.1
manufactured by HITACHI SEISAKUSHO Co., Ltd.) in chloroform as the
solvent at a temperature of 23.degree. C. and expressed as Mw/Mn of
the corresponding polystyrene.
[0080] (2) Pour Point
[0081] The pour point was measured in accordance with the method of
Japanese Industrial Standard K 2269.
[0082] (3) Kinematic Viscosity and Viscosity Index
[0083] The kinematic viscosity was measured in accordance with the
method of Japanese Industrial Standard K 2283. The viscosity index
was calculated from the kinematic viscosity in accordance with the
method of Japanese Industrial Standard K 2283.
Example 1
[0084] (1) Synthesis of
(1,1'-dimethylsilylene)(2,2'-isopropylidene)bis(in- denyl)zirconium
dichloride
[0085] (i) Into a three-necked flask which was purged with
nitrogen, 10.8 g (444 mmoles) of Mg and 45 ml of tetrahydrofuran
(THF) were placed and then 0.6 ml of 1,2-dibromomethane was added.
After the resultant mixture was stirred for 5 minutes, the solvent
was removed and then 200 ml of THF was added. A solution prepared
by dissolving 18.3 g (105 mmoles) of
.alpha.,.alpha.-dichloro-o-xylene in 300 ml of THF was added
dropwise to the obtained mixture at the room temperature over 3
hours. The reaction mixture was further stirred at the room
temperature for 15 hours.
[0086] The reaction mixture was cooled to -78.degree. C. and 100 ml
of a THF solution containing 6.6 g (36.2 mmoles) of diethyl
dimethylmalonate was added dropwise to the reaction mixture over 1
hour. After the resultant mixture was further stirred at the room
temperature for 2 hours, 100 ml of water was added. The obtained
reaction mixture was filtered under suction. After the solvent in
the filtrate was removed by distillation in vacuo, a 1 N aqueous
solution of ammonium chloride was added and the resultant mixture
was subjected to extraction with dichloromethane. The organic phase
was washed with 100 ml of water twice and dried with magnesium
sulfate. After the solvent was removed by distillation, a yellow
oily substance was obtained. The obtained substance was purified in
accordance with the column chromatography and recrystallized from
hexane and 4.8 g (the yield: 44%) of colorless crystals of compound
(1) were obtained.
[0087] The result of the measurement of .sup.1H-NMR was as
follows:
[0088] .sup.1H-NMR CDCl.sub.3) .delta.: 1.235 (s, 6H, CH.sub.3),
3.002 (d, J=16.4 Hz), 3.470 (d, J=16.4 Hz), (8H, CH.sub.2), 3.767
(s, 2H, OH) and 7.2 to 7.4 (m, 8H, PhH) 7
[0089] (Me represents methyl group; the same in the formulae shown
hereinafter.)
[0090] (ii) Compound (1) in an amount of 4.8 g (15.9 mmoles) was
dissolved in 30 ml of dichloromethane. To the resultant solution,
3.04 g (15.9 mmoles) of p-toluenesulfonic acid was added and the
mixture was heated under refluxing for 8 hours. The reaction
mixture was washed with an aqueous solution of sodium
hydrogencarbonate and water, successively, and dried with anhydrous
magnesium sulfate. After the solvent was removed by distillation, a
yellow oily substance was obtained. The obtained substance was
purified in accordance with the column chromatography and
recrystallized from hexane and 2.3 g (the yield: 54%) of compound
(2) was obtained.
[0091] The result of the measurement of .sup.1H-NMR was as
follows:
[0092] .sup.1H-NMR CDCl.sub.3) .delta.: 1.586 (s, 6H, CH.sub.3),
3.470 (s, 4H, CH.sub.2), 3.767 (s, 2H, CpH) and 6.9 to 7.5 (m, 8H,
PhH) 8
[0093] (iii) Into a Schlenk tube purged with nitrogen, 6.2 g (22.7
mmoles) of compound (2) and 50 ml of diethyl ether were placed.
[0094] The above solution was cooled at -78.degree. C. and 28.4 ml
(45.4 mmoles) of a solution of butyllithium (1.60 moles/liter) was
added dropwise. After the resultant mixture was stirred at the room
temperature for 3 hours, the supernatant liquid was removed and the
precipitates were washed twice with 20 ml of diethyl ether. After
being dried in vacuo, white powder of dilithium salt (3) was
obtained. 9
[0095] (iv) Dilithium salt (3) obtained above was dissolved in 100
ml of THF and 3.0 g (22.7 mmoles) of dichlorodimethylsilane was
added dropwise at the room temperature. After the resultant mixture
was stirred at the room temperature for 3 hours, the solvent was
removed by distillation and then 100 ml of water was added. The
aqueous phase was subjected to extraction with 200 ml of
dichloromethane and the organic phase was washed twice with water
and dried with anhydrous magnesium sulfate. After the solvent was
removed by distillation and the obtained solid substance was
recrystallized from hexane, 6.5 g (the yield: 86.5%) of colorless
crystals of compound (4) were obtained.
[0096] The result of the measurement of .sup.1H-NMR was as
follows:
[0097] .sup.1H-NMR (CDCl.sub.3) .delta.: -0.354 (s, 6H,
SiCH.sub.3), 1.608 (s, 6H, CCH.sub.3), 3.347 (s, 2H, SiCH), 6.785
(s, 2H, CpH) and 6.9 to 7.6 (m, 8H, PhH) 10
[0098] (v) Into a Schlenk tube purged with nitrogen, 0.9 g (2.7
mmoles) of compound (4) and 50 ml of hexane were placed. The above
solution was cooled at 0.degree. C. and 3.4 ml (5.4 mmoles) of a
solution of butyllithium (1.60 moles/liter) was added dropwise.
After the resultant mixture was stirred at the room temperature for
3 hours, the supernatant liquid was removed and the precipitates
were washed twice with 50 ml of hexane. After the remaining solid
substance was dried in vacuo, pink powder of dilithium salt (5) was
obtained. 11
[0099] (vi) To dilithium salt (5) obtained above, 50 ml of toluene
was added. To the obtained suspension, 20 ml of a suspension
containing 0.63 g (2.7 mmoles) of zirconium tetrachloride was added
dropwise at 0.degree. C. After the resultant mixture was stirred at
the room temperature for 24 hours, the precipitates were removed by
filtration and the filtrate was concentrated. After
recrystallization from a mixture of toluene and hexane, 0.24 g (the
yield: 19%) of yellowish orange crystals of compound (6) were
obtained.
[0100] The result of the measurement of .sup.1H-NMR was as
follows:
[0101] .sup.1H-NMR (CDCl3) .delta.: -0.172 (s, 3H, SiCH.sub.3),
0.749 (s, 3H, SiCH.sub.3), 1.346 (s, 3H, CCH.sub.3), 2.141 (s, 3H,
CCH.sub.3), 6.692 (s, 2H, CpH) and 6.9 to 8.1 (m, 8H, PhH) 12
[0102] (2) Polymerization of 1-octene
[0103] Into an autoclave made of stainless steel and having an
inner volume of 1 liter, which was dried sufficiently and purged
with nitrogen, 200 ml of 1-octene and 5 mmoles of methylaluminoxane
(as 2.5 ml of a heptane solution having a concentration of 2.0
mmoles/ml) were placed. Then, hydrogen was introduced so that the
pressure was adjusted at 0.2 MPaG and the temperature was raised to
65.degree. C. Into the reactor, 5 micromoles of
(1,1'-dimethylsilylene) (2,2'-isopropylidene)bis(indenyl)zi-
rconium dichloride (as 1 ml of a heptane solution having a
concentration of 5 micromoles/ml) was added and the polymerization
was started. After 30 minutes, 10 ml of methanol was added and the
polymerization was terminated. The content was taken out and solid
substances were removed by filtration through a filter paper 2C
manufactured by TOYO ROSHI Co., Ltd. From the obtained solution,
heptane, the raw materials of the reaction and methanol were
removed using a rotary evaporator (under a vacuum of about
1.0.times.10.sup.-4 MPa in an oil bath at 100.degree. C.) and 40 g
of a colorless transparent liquid was obtained. The results of
evaluation obtained in accordance with the methods described above
are shown in Table 1.
Example 2
[0104] The same procedures as those conducted in Example 1 were
conducted except that the pressure of hydrogen was adjusted at 0.7
MPaG and 62 g of a colorless transparent liquid was obtained. The
results of evaluation obtained in accordance with the methods
described above are shown in Table 1.
Example 3
[0105] The same procedures as those conducted in Example 1 were
conducted except that 1-dodecene was used in place of 1-octene, 10
mmoles of methylaluminoxane (as 5.0 ml of a hexane solution having
a concentration of 2.0 mmoles/ml) was used and 10 micromoles of
(1,1'-dimethylsilylene) (2,2'-isopropylidene)bis(indenyl)zirconium
dichloride (as 2 ml of a heptane solution having a concentration of
5 micromoles/ml) was used and 80 g of a colorless transparent
liquid was obtained. The results of evaluation obtained in
accordance with the methods described above are shown in Table
1.
Example 4
Hydrogenation of a Polymer of an .alpha.-olefin
[0106] (1) Preparation of a Catalyst
[0107] Into a 2 liter autoclave made of SUS 316 stainless steel,
100 g of nickel diatomaceous earth (manufactured by NIKKI KAGAKU
Co., Ltd.; N-113) and 300 ml of 2,2,4-trimethylpentane were placed.
After the autoclave was purged with hydrogen, the pressure of
hydrogen was raised to 2.0 MPaG and the temperature was raised to
140.degree. C. The autoclave was kept in this condition for 1 hour
and then cooled to the room temperature and a catalyst was
prepared.
[0108] (2) Hydrogenation
[0109] The autoclave containing the catalyst prepared above was
opened after being purged with nitrogen and 50 g of the polymer of
1-octene obtained in Example 2 was placed into the autoclave. After
the autoclave was purged with hydrogen, the pressure of hydrogen
was raised to 2.0 MPaG and the temperature was raised to
120.degree. C. The autoclave was kept in this condition for 2 hours
and then cooled to the room temperature. The autoclave was opened
after being purged with nitrogen and the reaction mixture was taken
out. The catalyst was removed from the reaction mixture by
filtration. From the obtained solution, 2,2,4-trimethylpentane was
removed using a rotary evaporator (under a vacuum of about
1.0.times.10.sup.-4 MPa in an oil bath at 100.degree. C.) and 47 g
of a colorless transparent liquid was obtained. The results of
evaluation obtained in accordance with the methods described above
are shown in Table 1.
1 TABLE 1 Example 1 Example 2 Example 3 Example 4 Number-average
2550 2080 3470 -- molecular weight (Mn) Weight-average 6830 3430
5920 -- molecular weight (Mw) Mw/Mn 2.68 1.65 1.71 -- Kinemtic
Viscosity 1620 382.3 419.0 389.0 (mm.sup.2/s at 40.degree. C.)
Kinemtic Viscosity 139.0 42.95 53.61 43.06 (mm.sup.2/s at
100.degree. C.) Viscosity index 192 168 195 166 Pour point
`.degree. C.) -37.5 -50.0 -25.0 -50.0
* * * * *