DESCRIPTION
ETHYLENE ·a-OLEFIN ·NON-CONJUGATED POLYENE COPOLYMER, USE THEREOF,
AND MANUFACTURING METHOD THEREOF
Technical Field
5 [0001]
The present invention relates to
ethylene·o:-olefin·non-conjugated polyene copolymers, uses
thereof, and manufacturing methods thereof.
Background Art
10 [0002]
Ethylene·a-olefin rubber, such as ethylene·propylene
copolymer rubber (EPR) and ethylene·propylene·diene copolymer
rubber (EPDM) , has no unsaturated bond in the main chain of the
molecular structure thereof and hence exhibits excellent heat
~: 15 aging resistance, weather resistance, and ozone resistance as
compared with general-purpose conjugated diene rubber, and has
been applied widely to uses, e.g., automobile components, wire
materials·, electric/electronic components, construction and
civil engineering materials, and industrial materials and
20 components.
[0003]
Conventionally, ethylene/a-olefin/non-conjugated polyene
copolymer rubber such as EPDM has been manufactured using a
catalyst system generally composed of a combination of a
SF-2890 2
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titanium-based catalyst or a vanadium-based catalyst and an
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organoaluminum compound (so-called Ziegler-Natta catalyst
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system) . The biggest disadvantage of this catalyst system is
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lower productivity in that it has a low polymerization activity
:''·ij 5 and a short catalyst life, which compel polymerization to be done
:-: at low temperatures in the order of 0 to 50°C. This poses a problem
;-:
of a high viscosity of a polymerization solution, which prevents
the olefin copolymer in a polymerizer from having a sufficiently
increased concentration, resulting in having a drawback-in that
10 the productivity is remarkably low. In addition, because of the
low polymerization activity, the copolymer will contain a lot of
catalyst residues at the completion of polymerization, and will
often not meet product performance requirements. Eliminating the
residues, then, requires a deashing process, which is remarkably
15 disadvantageous in production cost.
[0004]
On one hand, ethylene/a-olefin/non-conjugated polyene
copolymerization based on a polymerization catalyst including a
bridged metallocene compound having a biscyclopentadienyl group
':i
20 or a bisindenyl group as a ligand is disclosed (Japanese Patent
Application Laid-Open (JP-A} No. 2005-344101, JP-A No. H09-151205,
Japanese National-Phase Publication (JP-A) No. 2000-507635) .
This method provides the obtainable
ethylene/a-olefin/non-conjugated polyene copolymer with a higher
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SF-2890 3
molecular weight compared to the aforementioned Ziegler-Natta
catalyst system, but the molecular weight is not sufficiently high
yet for carrying out high-temperature polymerization. Generally,
in high-temperature solution polymerization, the viscosity of a
5 polymerization solution is lowered, which enables the olefin
copolymer in a polymeiizer to maintain its concentration high,
enhancing productivity per polymerizer. On the other hand,
however, it is well known to those of skill in the art that the
molecular weight of an olefin copolymer produced at an increased
10 polymerization temperature will decrease. Accordingly, in order
to manufacture an olefin copolymer with a desired high molecular
weight even in highly productive high-temperature polymerization,
a catalyst for producing a high molecular weight olefin copolymer
is needed.
15 [0005]
In products made of ethylene/~-olefin/non-conjugatect
polyene copolymer rubber such as EPDM, the content of a residual
polymerization sol vent or an unreacted olefin monomer is usually
controlled depending on the required performance for use. In
20 manufacturing facilities, elimination of these impurities is
generally carried out by operations such as heating and pressure
reduction in a post-polymerization process. For example, in the
manufacture of EPDM, a large amount of load is required for
elimination of unreacted non-conjugated polyene having a high
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SF-2890 4
boiling point, and hence a smaller amount of residual unreacted
non-conjugated polyene, as compared to EPDM, in a polymerization
solution discharged from a polymerization reactor will lead to
a more enhanced productivity. In other words, in cases where a
certain amount of EPDM is continuously manufactured during a
certain period of time, the smaller the amount of unreacted
non-conjugated polyene is, the lower the load of operations of
heating and pressure reduction is, allowing production cost to
be reduced. Conversely, in cases where the load of operations
of heating and pressure reduction is maintained constant, an
effect is given by which the smaller the amount of unreacted
non-conjugated polyene is, the larger the amount of production
per a certain period of time for manufacturing facilities is.
[0006]
Examples of a method for reducing the amount of unreacted
non-conjugateq polyene in a polymer~zation solut~on in orde_.r;: -~o
obtain such advantages include a method using a polymerization
catalyst having a high copolymerization performance for
non-conjugated polyene. Using such a polymerization catalyst
enables the amount added of non-conjugated polyene to be reduced
in manufacturing EPDM having a desired non-conjugated polyene
content, and an effect of reducing the amount of resulting residual
unreacted non-conjugated polyene can be achieved.
[0007]
SF-2890 5
As described above, a polymerization catalyst, which
produces an ethylene/a-olefin/non-conjugated polyene copolymer
with a high molecular weight to achieve a high productivity via
high-temperature polymerization, and which has a high
5 non-conjugated polyene copolymerization performance to enhance
productivity via reduCtion of load in a post-polymerization
process, is needed. In industry, above all, a polymerization
catalyst by which ·thes·e performances and a high polymerization
activity that does not require a deashing process are achieved
·:
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desired.
[0008]
In Patent Literature 1 (W02009/081792) and Patent
Literature 2 (W02009/081794), the present applicant proposes a
15 method for manufacturing an ethylene/a-olefin/non-conjugated
polyene· copolymer .using a catalyst including .. a specific bridged
cyclopentadienyl-fluorenyl metallocene compound. The
manufacturing method according to Patent Literature 1 allows an
ethylene/a-olefin/non-conjugated polyene copolymer having a high
20 molecular weight to be manufactured based on a favorable
polymerization activity and a favorable non-conjugated polyene
copolymerization ability, and the manufacturing method according
to Patent Literature 2 allows an
ethylene/a-olefin/non-conjugated polyene copolymer having a high
SF-2890 6
molecular weight to be manufactured based on a favorable
polymerization activity and a favorable non-conjugated polyene
copolymerization ability and further allows a polymerization
temperature to be set higher.
5 [0009]
In recent years, for the needs exploiting the excellent heat
resistance, weather resistance and flexibility of
ethylene· a-olefin rubber, raw material development and product
development for transparent bridged sheets have been carried out
10 vigorously.
[DOlO]
As a use of EPDM, for example, using EPDM to obtain a rubber
molded article for sealing is known (see, for example, Patent
Literature 3). Seal packings which are rubber molded articles
15 for sealing are used for various uses such as automobiles,
industrial machinery and electronic components, and since,
automobiles, industrial machinery and the like are used in a cold
area, the seal packings require mechanical strength at room
temperature as well as low-temperature properties.
20 [DOll]
As a use of EPDM, for example, it is known to use
ethylene·propylene·diene copolymer rubber (EPDM) as a rubber
component of a composition for forming a hose (Patent Literature
4). In a use in which a hose is used, for example, automobiles,
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SF-2890 7
use in a cold area is assumed, and thereby mechanical properties
{such as tensile strength) for room temperature as well as rubber
characteristics (such as rubber elasticity} for low temperature
are required.
5 [0012]
As a method for improving low-temperature flexibility and
heat aging resistance of ethylene·propylene·diene copolymer
rubber {EPDM), an ethylene·a-olefin·non-conjugated polyene
copolymer is proposed which uses a CcC10 a-olefin as an ct-olefin
10 and which has an excellent randomness of an ethylene and an
a-olefin (Patent Literature 5: JP-A No. H09-71617). It is
described in Example 4 of Patent Literature 5 that an ethylene
1-butene ENB copolymer was obtained, having a B value of 1.12 at
maximum, wherein the B value is an index indicating whether
15 randomness is acceptable or not, and is represented by the equation
below.
[0013]
B value ~ [EX] I (2 [E] • [X]) --- (i)
wherein [E] and [X] represent a mole fraction of an ethylene
20 and a C4-C20 a-olefin respectively in an
ethylene·a-olefin·non-conjugated polyene copolymer; and [EX]
represents an ethylene·C4-C20 a-olefin diad chain fraction.
In another case, it is disclosed in the examples of Patent
Literature 2 (W02009/081794) that an ethylene·propylene·ENB
SF-2890 8
copolymer having a B value of 1.11 to 1.24 was obtained using a
specific transition metal compound (bridged metallocene
compound), wherein the B value is indicative of randomness (but
is somewhat different in definition from the B value described
5 in Patent Literature 5) . In Patent Literature 2, however, the
mechanical properties Of an ethylene· propylene· ENB copolymer are
not described.
[0014]
[B value = {c + d) I [2 x a x (e + f)] --- [IV]
10 wherein a, e and fare an ethylene mole fraction, an a-olefin
mole fraction and a non-conjugated polyene mole fraction
respective~y of the ethylene/a-olefin/non-conjugated polyene
copolymer; c is an ethylene-a-olefin diad mole fraction; and d
is an ethylene-non-conjugated polyene diad mole fraction.
15 A bridged foam made from EPDM is used as a sound insulation
material for automobiles, electrical products, and the like. , For
example, it is known that EPDM or .a mixture of EPDM and_ EPR is
used as a rubber component of a composition for forming a sound
insulation material (Patent Literature 6 to 8).
20 [0015]
In this regard, in cross-linking and foaming a composition
including EPDM and manufacturing a cross-linked foam for use for
sound insulation materials, an EPDM having a favorable
foamability is preferably used. However, conventionally used
--_ ---- -- -" '-"------ -
SF-2890 9
EPDM having an excellent foamability has problems in that its roll
processability is not favorable and that a molded article formed
from the EPDM does not have sufficient sound insulation
performance.
5 [0016]
For this reason, butyl rubber is conventionally blended with
EPDM to improve roll processability. However, EPDM and butyl
rubber are different from each other in behavior in cross-linking.
Because of this, a composition including EPDM and butyl rubber
10 is difficult to control for cross-linking and foaming, and poses
a problem, for example 1 in that the specific gravity of the
obtainable molded article is large.
Citation List
Patent Literature
15 [0017]
Patent Literature 1: W02009/081792
Patent Literature 2: W02009/081794
Patent Literature 3: W02000/59962
Patent Literature 4 : JP-A No. H09-67485
20 Patent Literature 5: JP-A No. H09-71617
Patent Literature 6: JP-A No. 2001-2866
Patent Literature 7: JP-A No. 2001-192488
Patent Literature 8 : JP-A No. 2005-75964
Surrunary of Invention
SF-2890 10
Technical Problem
[0018]
Howeverr a conventional method for manufacturing an
ethylene/a-olefin/non-conjugated polyene copolymer, such as the
5 manufacturing methods disclosed in Patent Literature 1 and 2, has
<
' room for further imprOvement with regard to achieving three
possibilities at a high level at the same-tim~: increasing the
molecular weight of an ethylene/a-olefin/non-conjugated polyene
copolymer produced during high-temperature polymerization,
,.,
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10 enhancing the non-conjugated polyene copolymerization
performance, and producing an ethylene/a-olefin/non-conjugated
polyene copolymer via a high polymerization activity.
[0019]
In view of such problems of conventional techniques, a
15 problem to be solved by the present invention 1 consists in solving
the fol.:J.owing_problems _.(1) to (3) at a high level in a WE;!ll-balanced
(
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fl First, the problem ( 1) is to provide a method for
;'ii 20 manufacturing an ethylene/a-olefin/non-conjugated polyene ,_,
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copolymer having a high molecular weight. As aforementioned,
high-temperature solution polymerization has some advantages
such as enhanced productivity and reduced production cost, but
will result in the produced olefin polymer having a lowered
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SF-2890 11
molecular weight at the same time, and thus, according to a
manufacturing method using a conventional catalyst, it is
difficult to have a sufficiently high polymerization temperature.
To enjoy the advantage of high-temperature solution
5 polymerization by solving this problem, achievement of a method
~ i
f: capable of manufacturing an ethylene/a-olefin/non-conjugated
'
polyene copolymer having a high molecular weight even in
!-
high-temperature polymerization is desired.
[0021]
10 Next, the problem (2) is to provide a method for
[j manufacturing an ethylene/a-olefin/non-conjugated polyene
,,,,
lj copolymer based on a high non-conjugated polyene copolymerization
"~ ~I performance. Such a manufacturing method, in manufacturing an
tj
li olefin copolymer with a desired content of a non-conjugated
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15 polyene, enables the amount added of non-conjugated polyene to
be_ r.educed,- thereby ,re_ducing- .a residual amount of- unreacted . - ' - ' -
non-conjugated polyene in a polymerization solution and hence
providing the advantage of reducing load in eliminating the
residual amount in a post-polymerization process.
20 [0022]
Next, the problem (3) is to provide a method for
manufacturing an ethylene/a-olefin/non-conjugated polyene
copolymer based on a high polymerization activity. The high
polymerization activity not only reduces catalyst cost but also
-------
SF-2890 12
provides the advantage of making a deashing process unnecessary
because the catalyst residue in the
ethylene/a-olefin/non-conjugated polyene copolymer is reduced.
[0023]
5 In other words, a problem to be solved by the present
invention 1 is to proVide a method for manufacturing an
ethylene/a-olefin/noJ_1-COnjugated polyene copolymer that can
solve the abo~·epr~bl~~s ~(1), (2) and (3) at a high level in a
well-balanced manner at the same time; i.e., the method for
10 manufacturing an ethylene/a-olefin/non-conjugated polyene
copolymer that can achieve three possibilities at a high level
in a well-balanced manner at the same time: increasing the
molecular weight .of a copolymer produced during high-temperature
polymerization, enhancing non-conjugated polyene
15 copolymerization performance and producing a copolymer via a high
polymerization activity. Such a method can proVide and make
commercially available, at a significant production efficiency
and production cost in industry, an
ethylene/a-olefin/non-conjugated polyene copolymer having an
20 excellent performance as a processing material.
[0024]
A problem of the present invention 2 is to provide an
ethylene· a-olefin· non-conjugated polyene copolymer that,
compared with previously proposed
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SF-2890 13
ethylene·a-olefin·non-conjugated polyene copolymers, further
has a lower compression set at low temperature and flexibility
and that has an excellent balance between low-temperature rubber
elasticity and room temperature tensile strength.
5 [0025]
There are some problems with conventional seal packings:
ones made of EPDM have insufficient low-temperature properties;
and ones made of silicone rubber have excellent low-temperature
properties but have the sealing properties impaired by.
10 insufficient room-temperature strength and susceptibility to
cuts and cracks.
[0026]
A problem of the present invention 2-1 is to provide: a
composition for seal packings that is capable of forming a seal
15 packing having low-temperature properties and a mechanical
strength (strength and strain) compatible therewith; and a ~eal
packing formed from the composition.
[0027]
A problem of the present invention 2-2 is to achieve
20 compatibility between the processability of an uncross-linked
composition including an ethylene·a-olefin·non-conjugated
polyene copolymer and the sound insulation performance and
properties, such as specific gravity, of a molded article obtained
by cross-linking the composition.
-- · -_:_,•CC.oo,,_,~_,,·"--~:~-- -------·. ,- ---- - ---~---- .. --- ----~~--------·
SF-2890 14
[0028]
Considering the possibility that hoses are used also in a
cold area, hoses having both low-temperature properties and
mechanical properties are desired. For example, it is known that
5 using a hose-forming composition including EPDM with a lowered
ethylene content improVes the low-temperature properties of the
obtained hose, but that its tensile strength is decreased.
[0029]
A problem of the present invention 2-3 is to provide: a
10 composition for forming hoses that is capable of forming a hose
excellent in terms of low-temperature properties and mechanical
properties; and a hose formed from the composition.
Solution to Problem
[0030]
15 The present inventors have made intensive studies to solve
the aforementioned problems. As a result, they have founq an
ethylene· a-olefin· non-conjugated polyene copolymer that,
compared with previously proposed
ethylene· a-olefin· non-conjugated polyene copolymers, further
20 has a lower compression set at low temperature and flexibility
and that has an excellent balance between low-temperature rubber
elasticity and room temperature tensile strength, and have come
to complete the present invention 2.
[0031]
SF-2890 15
The present inventors have made intensive studies to solve
the aforementioned problems. As a result, they have found that
the aforementioned problems can be solved by using an
ethylene· a-olefin· non-conjugated polyene copolymer that,
5 compared with previously proposed
ethylene· a-olefin· non-conjugated polyene copolymers, has a lower
compression set at low temperature and flexibility and that has
an excellent balance of properties of low-temperature rubber
elasticity and room temperature tensile strength, and have come
10 to complete the present invention 2-1.
[0032]
The present inventors have made intensive studies to solve
the aforementioned problems. As a result, they have found that
the aforementioned problems can be solved by using a composition
15 including a specific ethylene·a~olefin·non-conjugated polyene
copolymer having a different B value, and have come to complete
the present invention 2-2.
[0033]
The present inventors have made intensive studies to solve
20 the aforementioned problems. As a result, they have found that
the aforementioned problems can be solved by using an
ethylene·a-olefin·non-conjugated polyene copolymer that,
compared with previously proposed ethylene a-olefin
non-conjugated polyene copolymers, has an excellent balance of
SF-2890 16
properties of low-temperature rubber elasticity and
room-temperature tensile strength, and have come to complete the
present invention 2-3.
[0034}
5 In other words, the present invention 2 relates to, for
example, the following (1] to [7]; the present invention 2-1
relates to, for example, the following [8] to [10]; the present
invention 2-2 relates to, for example, the following [11] to [15];
and the present invention 2-3 relates to, for example, . the
10 following [16] to [18}.
[0035}
The present invention 1 for solving the aforementioned
problems is a method for manufacturing an
ethylene/a-olefin/non-conjugated polyene copolymer based on an
~· 15 olefin polymerization catalyst including a bridged metallocene
compound having a specific fluorene structure.
[0036]
In other words, the present invention 1 relates to, for
example, the following [19] to [34] ,
20 [0037}
[1] An ethylene ·a-olefin ·non-conjugated polyene copolymer
including a structural unit derived from an ethylene [A], a
structural unit derived from a CrC20 a-olefin [B] and a structural
unit derived from a non-conjugated polyene [C], and satisfying
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SF-2890 17
the following (1) to (4):
(1) a molar ratio ([A] I [B]) of the structural units derived
from the ethylene [A] to the structural units derived from the
a-olefin [B] is 40/60 to 90/10;
5 (2) a content of the structural units derived from the
non-conjugated polyene [C] is 0.1 to 6.0 mol% based on the total
of the structural units of [A], [B] and _[C] as 100 mol%;
(3) a Mooney viscosity ML(1+4 l125°C at 125°C is 5 to 100; and
(4) a B value represented by the following formula. (i) is
10 1.20 or more.
[0038]
B value~ ([EX]+ 2[Y]) I [2' [E]' ([X]+ [Y])] --- (i),
wherein [E], [X] and [Y] represent a mole fraction of the
ethylene [A], the C4-C2o a-olefin [B] and the non-conjugated
;: 15 polyene [C] respectively, and [EX] represents an ethylene
!.'
[A] -C4-C20 a-olefin [B] diad chain fraction.
[2] The ethylene·a-olefin·non-conjugated polyene.
copolymer according to [1], wherein the C4-C20 a-olefin [B] is
1-butene.
20 [0039]
[3] The ethylene·a-olefin·non-conjugated polyene
copolymer according to [1] or [2], wherein the
ethylene·a-olefin·non-conjugated polyene copolymer is obtained
by copolymerizing an ethylene, a C4-C20 a-olefin and a
- -- • -~c~O-,_-.-
SF-2890 18
non-conjugated polyene in the presence of an olefin
polymerization catalyst containing:
(a) a transition metal compound represented by the
following general formula [VII]; and
5 lb I at least one compound selected from
(b-1) organometallic compounds,
(b-2) organoaluminum oxy-compounds, and·
(b--3) components which react with the transition
metal compound (a) to form an ion pair.
10 [0040]
[Chern. 1]
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SF-2890 19
wherein M is a titanium atom, a zirconium atom, or a hafnium
atom;
R5 and R6 are substituted aryl groups wherein one or more
of the hydrogen atoms of an aryl group are substituted with an
5 electron-donating substituent having a substituent constant o of
-0.2 or less in the Haminett 1 s rule; wherein when the substituted
aryl group has a plurality of the electron-donating substituents,
each ·of the electron-donating substituents may be the same or
different; wherein the substituted aryl group optionally includes
10 a substituent selected from C1-C20 hydrocarbon groups,
silicon-containing groups, nitrogen-containing groups,
oxygen-containing groups, halogen atoms and halogen-containj_ng
groups other than-the electron-donating substituents; and wherein
when the substituted aryl group includes a plurality of the
15 substituents, each of the substituents may be the same or
different;
Q is selected in an identical or different combination from
halogen atoms, C1-C20 hydrocarbon groups, anionic ligands and
neutral ligands capable of being coordinated with a lone electron
20 pair; and
j is an integer of 1 to 4.
[4] A cross-linked ethylene·a-olefin·non-conjugated
polyene copolymer, wherein the ethylene ·a-olefin ·non-conjugated
polyene copolymer according to any one of [11 to [3] is
SF-2890 20
cross-linked using a cross-linking agent.
[0041]
[5] A molded article formed using the
ethylene ·a-olefin ·non-conjugated polyene copolymer according to
5 any one of [l] to [3] or the cross-linked
ethylene ·a-olefin ·non-Conjugated polyene copolymer according to
I 4 I .
[0042]
[6] A composition including the
10 ethylene ·a-olefin ·non-conjugated polyene copolymer according to
any one of [1] to [3].
[0043]
[7] A method for manufacturing the
ethylene ·a-olefin ·non:-conj ugated polyene copolymer according to
15 any one of [1] to [3], wherein the ethylene, the CrC20 a-olefin
and the non-conjugated polyene are copolymerized in the presf!nce
of an olefin polymerization catalyst including:
I a) a transition metal compound represented by the
following general formula [VII]; and
20 (b) at least one compound selected from
(b-1) organometallic compounds,
{b-2) organoaluminum oxy compounds, and
(b-3) components which react with the transition
metal compound (a) to form an ion pair.
SF-2890 21
[0044]
[Chern. 2]
... [VII]
wherein M is a titanium atom, a zirconium atom, or a hafnium
5 atom;
R5 and R6 are substituted aryl groups wherein one or more
of the hydrogen atoms of an aryl group are substituted with an
electron-donating substituent having a substituent constant a of
-0.2 or less in the Hammett's rule; wherein when the substituted
10 aryl group has a plurality of the electron-donating substituents,
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each of the electron-donating substituents may be the same or
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different; wherein the substituted aryl group optionally contain
~j
M fl a substituent selected from C1-C20 hydrocarbon groups,
,".. ,
I
"fl silicon-containing groups, nitrogen-containing groups,
,,
i 15 oxygen-containing groups, halogen atoms and halogen-containing
•• 1
groups other than the electron-donating substi tuents; and wherein
when the substituted aryl group has a plurality of the substituents,
each of the substituents may be the same or different;
SF-2890 22
Q is selected in an identical or different combination from
halogen atoms, C1-C20 hydrocarbon groups, anionic ligands and
neutral ligands capable of being coordinated with a lone electron
pair; and
5 j is an integer of 1 to 4.
[8] A compositioD for a seal packing, wherein the
composition includes the ethylene·a-olefin·non-conjugated
polyene copolymer according to any one of [l] to [3].
[0045]
10 [9] A seal packing formed using the composition for a seal
packing according to [8).
[0046]
[10] The seal packing according to [9], wherein the seal
packing is a seal component for automobiles, a seal component for
15 machinery, a seal component for electronic and electrical
i: components, a gasket for construction, or a seal component~ for
civil engineering and building materials.
[0047]
[11] A composition including:
20 an ethylene·a-olefin·non-conjugated polyene copolymer {1) and
an ethylene·a-olefin·non-conjugated polyene copolymer (2)
including a structural unit derived from ethylene [A 1 ], a
structural unit derived from a CrC20 a-olefin [B'] and a structural
unit derived from a non-conjugated polyene [C'], and satisfying
SF-2890 23
the following (I):
(I) the B value represented by the following equation (i)
is less than 1.20;
wherein the ethylene ·a-olefin ·non-conjugated polyene copolymer
5 (1) is the ethylene ·a-olefin ·non-conjugated polyene copolymer of
any one of [ 1] to [ 3] .
[0048]
B value ~ I [EX] + 2 [Y]) I (2 • [E] • I [X] + [Y])} --- (i)
wherein [E], [X] and [Y] represent a mole fraction of the
10 ethylene [A'], the C3-C20 a-olefin [B'] and the non-conjugated
polyene [C'] respectively, and [EX] represents an ethylene
[A' ]-C3-C20 a-olefin [B'] diad chain fraction.
[12] The composition according to [11], wherein a mass ratio
[{1)/(2)] of the ethylene·a-olefin·non-conjugated polyene
15 copolymer (1) to the ethylene·a-olefin·non-conjugated polyene
copolymer (2) is 10/90 to 50/50.
[0049]
[13] A cross-linked material obtained by cross-linking the
composition according to [11] or [12].
20 [0050]
[14] A cross-linked foam obtained by cross-linking and
foaming the composition according to [11] or [12].
'.1
[0051]
[15] A sound insulation material obtained from the
· .
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SF-2890 24
composition according to [11] or [12].
[0052]
[16] A composition for forming a hose, wherein the
composition includes the ethylene·a-olefin·non-conjugated
5 polyene copolymer according to any one of [1] to [3] .
10
[0053]
[17] A hose having a lay~r formed by cross-linking treatment
of the composition according to "['16] for forming a hose.
[0054]
[18] The hose according to [17], wherein the hose is used
for any of uses for automobiles 1 motorbikes 1 industrial machinery,
construction machinery or agricultural machinery.
[0055]
[19] A method for manufacturing an
15 ethylene/a-olefin/non-conjugated polyene copolymer, the method
including copolymerizing an ethylene, an a-olefin havi.ng trree
or more carbon atoms and a non-conjugated polyene in the presence
of an olefin polymerization catalyst containing:
(a)_ a transition metal compound represented by the
20 following general formula [I]; and
(b) at least one compound selected from
(b-1) organometallic compounds,
(b-2) organoaluminum oxy-compounds, and
(b-3) components which react with the transition
SF-2890 25
metal compound (a) to form an ion pair.
[0056]
[Chern. 3]
. .. [ I]
5 wherein Y is selected from a carbon atom, a silicon atom,
a germanium atom and a tin atom;
M ~s a titanium .atom, a zi.rconi1..1m atom .or a hafnium atom;
R1
, R2
, R3
, R4, R5 and R6, each of which may be- the- _same or
different, are atoms or substituents selected from hydrogen atoms,
10 C1-C20 hydrocarbon groups, aryl groups, substituted aryl groups,
fI.
II
II
silicon-containing groups, nitrogen-containing groups,
oxygen-containing groups, halogen atoms and halogen-containing
groups;
adjacent substituents between R1 and R6 are optionally bound
15 together to form a ring;
SF-2890 26
Q is selected in an identical or different combination from
halogen atoms, C1-C20 hydrocarbon groups, anionic ligands and
neutral ligands capable of being coordinated with a lone electron
pair;
5 n is an integer of 1 to 4; and
j is an integer ·of 1 to 4.
[20] The method for manufacturing an
ethylene/ex-olefin/non-conjugated polYene copolymer according to
[19], wherein n in the general formula [I] is 1.
10 [0057]
[21] The method for manufacturing an
ethylene/ex-olefin/non-conjugated polyene copolymer according to
[19] or [20], wherein R1
, R2
, R3 and R4 in the general formula [I]
are all hydrogen atoms.
15 [0058]
[22] The method for man_ufacturing an.
ethylene/a-olefin/non-conjugated polyene copolymer according to
any one of [19] to [21], wherein Y in the general formula [I] is
a carbon atom.
20 [0059]
[23] The method for manufacturing an
ethylene/a-olefin/non-conjugated polyene copolymer according to
any one of [ 19] to [22], wherein R5 and R6 in the general formula
[I] are groups selected from aryl groups and substituted aryl
-- ------~----·---------
SF-2890 27
groups.
[0060]
[24) The method for manufacturing an
ethylene/a-olefin/non-conjugated polyene copolymer according to
5 [23], wherein R5 and R6 in the general formula [I] are substituted
aryl groups wherein one or more of the hydrogen atoms of an aryl
group are substituted with an electron-donating substituent
having a substituent constant a of -0.2 or less in the Hammett's
rule; wherein when the substituted aryl group has a plura-lity of
10 the electron-donating substituents, each of the
electron-donating substituents may be the same or different;
wherein the substituted aryl groups optionally contain a
substituent selected from C1-C20 hydrocarbon groups,
silicon-containing groups, nitrogen-containing groups 1
15 oxygen-containing groups, halogen atoms and halogen-containing
!. groups other than the electron-donating substituents; and whe;rein
when the substituted aryl group has a plurality of the substi tuents,
each of the substituents may be the same or different.
[0061]
20 [25] The method for manufacturing an
ethylene/a-olefin/non-conjugated polyene copolymer according to
[24], wherein the electron-donating substituent is a group
selected from nitrogen-containing groups and oxygen-containing
groups.
SF-2890 28
[0062]
[26] The method for manufacturing an
ethylene/et-olefin/non-conjugated polyene copolymer according to
[25] r wherein R5 and R6 in the general formula [I] are substituted
5 phenyl groups in which a group selected from the
nitrogen-containing groups and the oxygen-containing groups is
contained in the meta position and/or para position to the bond
toY.
·::
>i
[0063]
~~ 10 [27] The method for manufacturing an
:;
ii
i
ethylene/a-olefin/non-conjugated polyene copolymer according to
:i
!
[26] 1 wherein R5 and R6 in the general formula [I] are substituted
ii
H phenyl groups including a nitrogen-containing group represented
by the following general formula [II] as the electron-donating
15 substituent.
[0064]
[Chern. 4]
• • • [I I]
wherein R7 and R8
, each of which may be the same or different
20 and may be bound together to form a ring, are atoms or substituents
' '
SF-2890 29
selected from hydrogen atoms, C1-C20 hydrocarbon groups,
silicon-containing groups, oxygen-containing groups and
halogen-containing groups; and the line on the right of N
represents a bond to a phenyl group.
5 [28] The method for manufacturing an
ethylene/a-olefin/non--conjugated polyene copolymer according to
[26], wherein R5 and R6 in the general formula [I} are substituted
phenyl groups including an oxygen-containing group represented
by the following general formula [III] as the electron-donating
10 substituent.
[0065]
[Chern. 5]
[III]
wherein R9 is an atom or a substituent selected from hydrogen
t: 15 atoms 1 C1-C2o hydrocarbon groups, silicon-containing groups, .
nitrogen-containing groups and halogen-containing groups; and
the line on the right of 0 represents a bond to a phenyl group.
[29] The method for manufacturing an
ethylene/C:t-olefin/non-conjugated polyene copolymer according to
20 any one of [19] to [28] 1 wherein M in the general formula (I] is
a hafnium atom.
[0066]
:!
u
SF-2890 30
[30] The method for manufacturing an
ethylene/o:-olefin/non-conjugated polyene copolymer according to
any one of [19] to [29], wherein the a-olefin is a CrC10 a-olefin.
[0067]
5 [31] The method for manufacturing an
ethylene/a-olefin/non--conjugated polyene copolymer according to
any one of [19) to [30], wherein the o:-olefin is at least one
selected from propylene and a 1-butene.
[0068 I
10 [32] The method for manufacturing an
ethylene/a-olefin/non-conjugated polyene copolymer according to
any one of [19] to [31], wherein the non-conjugated polyene is
represented by the following general formula [IV].
[0069]
15 [Chem. 6]
R1o
t'Y'--....R 11
~R12
R13
wherein n is an integer of 0 to 2;
. . ' [IV]
R10
, R11 , R12 and R13 , each of which may be the same or different,
SF-2890 31
are atoms or substituents selected from hydrogen atoms, C1-C20
hydrocarbon groups, silicon-containing groups,
nitrogen-containing groups, oxygen-containing groups, halogen
atoms and halogen-containing groups, which hydrocarbon groups
5 optionally contain a double bond;
two optional substituents of R10 to R13 are optionally bound
together to form a ring which optionally contains a double bond,
R10 and R11 , or R12 and R1j optionallY' l~rro" an .alkylidene g~ciup,
R10 and R12
, or R11 and R13 are optionally bound together to form
10 a double bond; and
at least one requirement of the following {i) to (iv) is satisfied:
(i} at least one of R10 to R13 is a hydrocarbon group having
one or more double bonds;
(ii) two optional substituents of R10 to R13 are bound
[i 15 together to form a ring and the- ring contains a double bond;
t
(iii) R10 and -R11
, or R12
· and R1_~, _ :form an al ky lidene group;
and
(iv) R10 and R12
, or R11 and R13 , are bound together to form
a double bond.
20 [33] The method according for manufacturing an
ethylene/0!-olefin/non-conjugated polyene copolymer to any one of
[19] to [32], wherein the non-conjugated polyene is
5-ethylidene-2-norbornene (ENB) or 5-vinyl-2-norbornene (VNB).
[0070]
'----- _,
SF-2890 32
[34] The method for manufacturing an
ethylene/a-olefin/non-conjugated polyene copolymer according to
any one of [19] to [33], wherein a polymerization temperature is
8 0°C or more.
5 Advantageous Effects of Invention
[0071]
The method according to the present invention 1 for
copolymerizing an ethylene, an a-olefin -and a non-conjugated
polyene in the presence of an olefin polymerization catalyst
10 including a bridged metallocene compound having a specific
fluorene structure can achieve the following effects (1) to (3)
at a high level in a well-balanced manner at the same time, thereby
enabling an ethylene/a-olefin/non-conjugated polyene copolymer
having an excellent performance as a processing material to be
15 manufactured at high productivity and low cost, so that a very
large and St;Lperior contribution is made to industry.
[0072]
Effect (1): an ethylene/a-olefin/non-conjugated polyene
copolymer having a high molecular weight can be manufactured.
20 This makes it possible to maintain, at a desired high value, the
molecular weight of an ethylene/0!-olefin/non-conjugated polyene
copolymer produced even in high temperature polymerization, and
thereby enables high temperature polymerization to be carried out.
In particular, in high temperature solution polymerization, the
SF-2890 33
viscosity of a polymerization solution including the produced
copolymer is lowered, thereby enabling the concentration of the
copolymer in a polymerizer to be increased compared with that in
low temperature polymerization, resulting in a significantly
5 enhanced productivity per polyrnerizer. Further, carrying out
high temperature polymerization reduces a heat removal cost for
a polymerizer significantly.
[0073]
Effect (2) : an ethylene/a-olefin/non-conjugated polyene
::
10 copolymer can be manufactured at a high non-conjugated polyene
copolymerization performance. Accordingly, in manufacturing an
olefin copolymer containing a desired non-conjugated polyene
content, the amount added of non-conjugated polyene can be reduced,
resulting in a reduced amount of residual unreacted
15 non-conjugated polyene in a polymerization solution, and the
advantage that load is lowered in removing the residue in~a
post-polymerization process can be obtained, leading to enhanced
productivity.
[0074]
20 Effect (3): an ethylene/a-olefin/non-conjugated polyene
copolymer can be manufactured at a high polymerization activity.
This not only reduces a catalyst cost but also reduces a catalyst
residue in the ethylene/a-olefin/non-conjugated polyene
copolymer, thereby making a deashing process unnecessary, and the
I,,I
SF-2890 34
;,,'
:I
'i
'!
advantage that the production cost is reduced can be obtained.
:1 [ 007 5]
!I'
I
'! Because the ethylene·a-olefin·/non-conjugated polyene
:! copolymer of the present invention 2 has a small compression set
5 at low temperature as well as flexibility and has an excellent
balance between low temperature rubber elasticity and room
temperature tensile strength, a composition having the
ethylene·a-olefin·non-conjugated polyene copolymer can
preferably be used for various uses, utilizing such properties.
10 [0076]
According to the present invention 2-1, there can be
provided a composition for seal packings that is capable of forming
a seal packing excellent in terms of low temperature properties,
such as low temperature flexibility, and mechanical properties,
15 such as tensile strength; and a seal packing formed from the
composition.
[0077]
According to the present invention 2-2, compatibility can
be achieved between the processability of an uncross-linked
20 composition including an ethylene·a-olefin·non-conjugated
polyene copolymer and the sound insulation performance and
properties, such as specific gravity, of a molded article obtained
by cross-linking the composition.
[0078]
SF-2890 35
According to the present invention 2-3, there can be
provided a composition for forming hoses that is capable of forming
a hose excellent in terms of low-temperature properties, such as
low temperature rubber elasticity, and mechanical properties,
5 such as room temperature tensile strength; and a hose formed from
the composition.
Brief Description of Drawings
[0079]
[Fig. 1] Fig. 1 is a chart showing the sound transmission
10 losses (dB) at 500 to 5000Hz for the tabular sponges obtained in
'<: ' ~1'
Example Dl and Comparative Example Dl.
;j
II
I
,l
"
Description of Embodiments
~ :'!
[0080]
:i
The present invention will be described in further detail.
15 Below, the present invention 1 1 the present invention 2, the
present inventions 2-1, 2-2, and 2-3 will be described in -this
order.
[0081]
(Present Invention 1]
20 The method according to the present invention 1 for
manufacturing an ethylene/a-olefin/non-conjugated polyene
copolymer is characterized by copolymerizing an ethylene, an
a-olefin having three or more carbon atoms, and a non-conjugated
polyene in the presence of an olefin polymerization catalyst
, -~ c- , " ________ , '-'---"--'-------' ~-- -----~---- -
SF-2890 36
including the transition metal compound (a) represented by the
general formula [I] and the compound (b) .
[0082]

5 The transition metal compound (a) is represented by the
general formula [I]. The transition metal compound (a) is a
metallocene compound having a bridged structure in the molecule,
i.e., a bridged metallocene compound.
[0083]
10 [Chem. 71
' :j
''
i-
L
i
I' ,(·,i'
!-.1
I
I
It r
. .. [ I]
i I wherein Y is selected from a carbon atom, a silicon atom,
;_li
I
'
a germanium atom and a tin atom;
'' '
' ' M is a titanium atom, a zirconium atom or a hafnium atom;
15
SF-2890 37
different, are atoms or substituents selected from hydrogen atoms,
C1-C20 hydrocarbon groups, aryl groups, substituted aryl groups,
silicon-containing groups, nitrogen-containing groups,
oxygen-containing groups, halogen atoms and halogen-containing
5 groups;
adjacent substituents between R1 and R6 may be bound together
to form a ring;
Q is selected in the same or different combination from
halogen atoms, C1-C20 hydrocarbon groups, anionic ligands and
10 neutral ligands capable of being coordinated with a lone electron
pair;
n is an integer of 1 to 4; and
j is an integer of 1 to 4.
Y, M, R1 to R6, Q, n and j in the formula [I] will be described
15 below.
[0084]
The transition metal compound (a) can also be used_in the
present inventions 2, 2-1, 2-2 and 2-3 and accordingly these
inventions may be described in the description of the transition
20 metal compound (a) .
[0085]
(Y, M, R1 to R6, Q, nand j)
Y is selected from a carbon atom, a silicon atom, a germanium
atom and a tin atom, and is preferably a carbon atom.
SF-2890 38
[0086]
M is a titanium atom, a zirconium atom or a hafnium atom,
and is preferably a hafnium atom.
[0087]
5 R1
, R2
, R3
, R4
, R5 and R6
, each of which may be the same or
different, are atoms or· substi tuents selected from hydrogen atoms,
C1-C20 hydrocarbon groups, aryl groups, substituted aryl groups,
. . .
silicon-cont.aiTii~g groups, nitrogen-corlfainirig groups,.
oxygen-containing groups, halogen atoms and halogen-containing
10 groups. The adjacent substituents between R1 and R6 are
optionally bound together to form a ring or are optionally not
unbound together.
[0088]
Here, examples of the C1-C20 hydrocarbon groups include a
15 C1-C20 alkyl group, a CrC20 cyclic saturated hydrocarbon group,
a C2-C20 chain un. saturated hydr- o. ca-rbon- group and a CrC20 cyplic •' . ,• .'- '· -
unsaturated hydrocarbon group. If adjacent substi tuen-ts of R1
to R6 are bonded to each other to form a ring, a C1-C20 alkylene
group, a C6-C20 arylene group, etc. can be given as examples.
20 [0089]
Examples of the C1-C20 alkyl groups include methyl group,
ethyl group, n-propyl group, allyl group, n-butyl group, n-pentyl
': group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl
group and n-decanyl group that are straight-chain saturated
::
'!
'i
::
:1 ::
li
,:
·SF-2890 39
hydrocarbon groups, and isopropyl group, isobutyl group, s-butyl
group, t-butyl group, t-amyl group, neopentyl group,
3-methylpentyl group, 1,1-diethylpropyl group,
1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group,
5 1,1-dipropylbutyl group, 1,1-dimethyl-2-methylpropyl group,
1-methyl-1-isopropyl-2-methylPropyl group and
cyclopropylmethyl group that are branched saturated hydrocarbon
groups. The number of -carbon atoms of the alkyl group is
preferably 1 to 6.
10 [0090)
Examples of the CrC20 cyclic saturated hydrocarbon groups
include cyclopropyl group, cyclobutyl group, cyclopentyl group,
cyclohexyl group, cycloheptyl group, cyclooctyl group,
norbornenyl group, 1-adamantyl group and 2-adamantyl group that
15 are cyclic saturated hydrocarbon groups, and 3-methylcyclopentyl
group, 3-methylCycohexyl , group,_-_ 4-methyJ,cyc_lohexyl group,
4-cyclohexylcyclohexyl group and 4-phenylcyclohexyl group that
are groups wherein a hydrogen atom of a cyclic saturated
hydrocarbon group is substituted by a C1-C17 hydrocarbon group.
20 The number of carbon atoms of the cyclic saturated hydrocarbon
group is preferably 5 to 11.
[0091]
Examples of the CrC20 chain unsaturated hydrocarbon groups
include ethenyl group (vinyl group), 1-propenyl group, 2-propenyl
I'' --------------------
;:
' \'
' '
i
il
'
L'I
t:
SF-2890 40
group (allyl group) and 1-methylethenyl group (isopropenyl group)
that are alkenyl groups, and ethynyl group, 1-propynyl group and
2-propynyl group (propargyl group} that are alkynyl groups. The
number of carbon atoms of the chain unsaturated hydrocarbon group
5 is preferably 2 to 4.
[0092]
Examples of the CrC20 cyclic unsaturated hydrocarbon groups
include cyclopentadienyl·grOup, norbornyl group, phenyl group,
naphthyl group, indenyl group, azulenyl group, phenanthryl group
10 and anthracenyl group that are cyclic unsaturated hydrocarbon
groups, 3-methylphenyl group {m-tolyl group), 4-methylphenyl
group (p-tolyl group), 4-ethylphenyl group, 4-t-butylphenyl
group, 4-cyclohexylphenyl group, biphenylyl group,
3,4-dimethylphenyl group, 3,5-dimethylphenyl group and
[_: 15 2, 4, 6-trimethylphenyl group (mesityl group) that are groups
wherein a hydrogen atom of a cyclic unsaturated hydrocarbon group
is substituted by a C1-C15 hydrocarbon group, and benzyl group and
curnyl group that are groups wherein a hydrogen atom of a
straight-chain hydrocarbon group or a branched saturated
20 hydrocarbon group is substituted by a cyclic saturated
hydrocarbon group or a C3-C19 cyclic unsaturated hydrocarbon group.
The number of carbon atoms of the cyclic unsaturated hydrocarbon
group is preferably 6 to 10.
[0093]
SF-2890 41
Examples of the C1-C20 alkylene groups include methylene
group, ethylene group, dimethylmethylene group (isopropylidene
group), ethylmethylene group, 1-methylethylene group,
2-methylethylene group, 1,1-dimethylethylene group,
5 1, 2-dimethylethylene group and n-propylene group. The number of
carbon atoms of the alkylene group is preferably 1 to 6.
[0094]
Examples of the C6-C20 arylene groups include o-phenylene
group, m-phenylene group, p-phenylene group and 4, 4' -biphenylene
10 group. The number of carbon atoms of the arylene group is
preferably 6 to 12.
[0095]
Examples of the aryl groups, part of which overlap with the
above-mentioned examples set forth for the C3-C20 cyclic
15 unsaturated hydrocarbon groups, include phenyl group, 1-naphthyl
group, 2-naphthyl group, anthracenyl group, phenanthrenyl group,
tetracenyl group, chrysenyl group, pyrenyl group, indenyl group,
azulenyl group, pyrrolyl group, pyridyl group, furanyl group and
thiophenyl group that are substituents derived from aromatic
'~I.' :' 20 compounds. As the aryl group, a phenyl group or a 2-naphthyl group
is preferable.
[0096]
Examples of the aromatic compounds include benzene,
naphthalene, anthracene, phenanthrene, tetracene, chrysene,
!
i
I
I',,
SF-2890 42
pyrene, pyrene, indene, azulene, pyrrole, pyridine, furan and
thiophene that are aromatic hydrocarbons and heterocyclic
aromatic compounds.
[0097]
5 Examples of the substituted aryl groups, part of which
overlap with the above-mentioned examples set forth for the CrC20
cyclic unsaturated hydrocarbon groups, include groups wherein one
or more hydrogen atoms possessed by the above aryl groups are
substituted by substituents selected from C1-C20 hydrocarbon
10 groups, aryl groups, silicon-containing groups,
nitrogen-containing group, oxygen-containing groups, halogen
atoms and halogen-containing groups, and specific examples
thereof include 3-methylphenyl group (m-tolyl group),
4-rnethylphenyl group (p-tolyl group), 3-ethylphenyl group,
15 4-ethylphenyl group, 3,4-dimethylphenyl group,
3,5-dimethylphenyl group, biphenylyl grpup,
4-(trimethylsilyl)phenyl group, 4-aminophenyl group,
4-(dimethylamino)phenyl group, 4-(diethylamino)phenyl group,
4-morpholinylphenyl group, 4-methoxyphenyl group,
20 4-ethoxyphenyl group, 4-phenoxyphenyl group,
3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group,
3-methyl-4-methoxyphenyl group, 3,5-dimethyl-4-methoxyphenyl
group, 3-(trifluoromethyl)phenyl group,
4-(trifluoromethyl)phenyl group, 3-chlorophenyl group,
SF-2890 43
4-chlorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group,
5-methylnaphthyl group and 2-(6-methyl)pyridyl group.
For the substituted aryl group, "electron-donating
group-containing substituted aryl group" provided later can be
5 mentioned.
[0098]
Examples of the silicon-containing groups include
alkylsilyl groups, such as trimethylsilyl group, triethylsilyl
group, t-butyldimethylsilyl group and triisopropyl group,
10 arylsilyl groups, such as dimethylphenylsilyl group,
methyldiphenylsilyl group and t-butyldiphenylsilyl group,
pentamethyldisilanyl group and trimethylsilylmethyl group, all
of which are groups wherein a carbon atom in a C1-C20 hydrocarbon
group is substituted by a silicon atom. The number of carbon atoms
15 of the alkylsily_l group is preferably 1 to 10, and the number of
carbon atoms of the ary_lsily_l group is preferably 6 to 18,
),
"~:
j:'
[0099]
h,,
\j
Examples of the nitrogen-containing groups include amino
t1
;! group, nitro group and N-morpholinyl group; and dimethylamino
;"i
':' 20 group, diethylamine group, dimethylaminomethyl group, cyano
group, pyrrolidinyl group, piperidinyl group and pyridinyl group
that are groups wherein in the aforesaid C1-C20 hydrocarbon groups
or silicon-containing groups, a =CH- structure unit is
substituted by a nitrogen atom, or a -CH2 - structure unit is
"
'
; !
~-:
:<
SF-2890 44
substituted by a nitrogen atom to which a C1-C20 hydrocarbon group
has been bonded, or a -CH3 structure unit is substituted by a
nitrogen atom to which a C1-C20 hydrocarbon group has been bonded
or a nitrile atom. As the nitrogen-containing group, a
5 dimethylamino group or a N-morpholinyl group is preferable.
[0100]
Examples of the oxygen-containing groups include hydroxyl
group; and methoxy group, ethoxy group, t-butoxy group, phenoxy
group, trimethylsiloxy group, methoxyethoxy group, hydroxymethyl
10 group1 methoxymethyl group, ethoxymethyl group, t-butoxymethyl
group, 1-hydroxyethyl group, 1-methoxyethyl group, 1-ethoxyethyl
group, 2-hydroxyethyl group, 2-rnethoxyethyl group, 2-ethoxyethyl
group, n-2-oxabutylene group, n-2-oxapentylene group,
n-3-oxapentylene group, aldehyde group, acetyl group, propionyl
15 group, benzoyl group, trimethylsilylcarbonyl group, carbamoyl
group, methylaminocarbonyl group, carboxyl grQup,
methoxycarbonyl group, carboxymethyl group, ethocarboxymethyl
group, carbamoylmethyl group, furanyl group and pyranyl group
that are groups wherein in the aforesaid C1-Czo hydrocarbon groups,
20 silicon-containing groups or nitrogen-containing groups, a -CH2 -
structure unit is substituted by an oxygen atom or a carbonyl group,
or a -CH3 structure unit is substituted by an oxygen atom to which
a C1-C20 hydrocarbon group has been bonded. As the
oxygen-containing group, a methoxy group is preferable.
',,
~!
SF-2890 45
[0101]
Examples of the halogen atoms include fluorine, chlorine,
bromine and iodine that are Group 17 elements.
[0102]
5 Examples of the halogen-containing groups include
trifluoromethyl group, tribromomethyl group, pentafluoroethyl
group and pentafluorophenyl group that are groups wherein in the
aforesaid cl·_:.c20 hydrOCarbon grOUpS, Si.liCQ!"{-COTitaining grOUpS I
nitrogen-containing groups or oxygen-containing groups, a
10 hydrogen atom is substituted by a halogen atom.
[0103]
Q is selected from a halogen atom, a C1-C2o hydrocarbon group,
an anionic ligand.and a neutral ligand capable of being coordinated
with a lone electron pair, in a combination of the same or different
15 kinds.
[0104]
Details of the halogen atom and the C1-C2o hydrocarbon group
are as previously described. When Q is a halogen atom1 it is
preferably a chlorine atom. When Q is a C1-C2o hydrocarbon group,
20 the number of carbon atoms of the hydrocarbon group is preferably
1 to 7.
[0105]
Examples of the anionic ligands include alkoxy groups, such
as methoxy group, t-butoxy group and phenoxy group, carboxylate
--------------
SF-2890 46
groups, such as acetate and benzoate, and sulfonate groups, such
as mesylate and tosylate.
[0106]
Examples of the neutral ligands capable of being coordinated
5 with a lone electron pair include organophosphorus compounds,
such as triffiethylphosphine, triethylphosphine,
triphenylphosphine and diphenylmethylphosphine, and ether
compounds, such as tetrahydrofuran, diethyl ether, dioxane and
1,2-dimethoxyethane.
10 [0107]
n is an integer of 1 to 4.
j is an integer of 1 to 4, and is preferably 2.
The above-mentioned examples set forth regarding the
formula [I] will apply in the same manner also in descriptions
15 that will be provided below for the present invention 1.
[0108]
The present inventors have intensively studied various
transition metal compounds and, as a result 1 have found for the
first time that when the transition metal compound (a) represented
20 by the general formula [I] contains, among others, a
2,3,6, 7-tetramethyl fluorenyl group in its ligand structure and
when an ethylene, an a-olefin having three or more carbon atoms,
and a non-conjugated polyene are copolymerized in the presence
of an olefin polymerization catalyst including the transition
I,
'I \1
lj
II
II
'I
F"
;,
!!
SF-2890 47
metal compound (a), an ethylene/a-olefin/non-conjugated polyene
copolymer with a high molecular weight or the below-mentioned
ethylene-based copolymer A can be manufactured based on the high
non-conjugated polyene copolymerization performance and the high
5 polymerization activity.
[0109]
The 2,3,6,7-tetramethyl fluorenyl group contained in the
transition metal compound {a) represented by the general formula
[I] has four substituents at its 2, 3, 6 and 7 position, hence
10 having a large electronic effect, and from this it is inferred
that this results in a high polymerization activity, causing an
ethylene/a-olefin/non-conjugated polyene copolymer with a high
molecular weight or the below-mentioned ethylene-based copolymer
A to be produced. Since a non-conjugated polyene is generally
15 bulky compared with an ex-olefin,~ it is inferred that especially
when· in a polymerization __ catalys~ for polyme_rizing it, th~
vicinity of the central metal of a metallocene compound, which
vicinity corresponds to a polymerization activity point, is less
bulky, it leads to an increase in the copolymerization performance
20 of the non-conjugated polyene. Because the four methyl groups
contained in the 2 1 3,6,7-tetramethyl fluorenyl group are not
bulky compared with other hydrocarbon groups, this is considered
to contribute to a high non-conjugated polyene copolymerization
performance. From the above1 it is inferred that the transition
SF-2890 48
metal compound (a) represented by the general formula [I]
including a 2,3,6,7-tetramethyl fluorenyl group in particular
achieves a high molecular weight of the produced
ethylene/a-olefin/non-conjugated polyene copolymer or the
5 below-mentioned ethylene-based copolymer A, a high
non-conjugated polyene- copolymerization performance and a high
polymerization activity at a high level in a well-balanced manner
at the same time.
[0110]
10 In the transition metal compound (a) represented by the
general formula [I], n is preferably 1. Such a transition metal
compound (a-1) is represented by the following genetal formula
[V] .

CLAIMS
1. An ethylene·a-olefin·non-conjugated polyene copolymer
comprising a structural unit derived from an ethylene [A], a
5 structural unit derived from a C4-C20 a-olefin [B] and a structural
unit derived from a non-conjugated polyene [C], and satisfying
the following (1) to (4):
(1) a molar ratio ([A] I [B]) of the structural units derived
from the ethylene [A] to the structural units derived from the
10 a-olefin [B] is 40/60 to 90/10;
(2) a content of the structural units derived from the
non-conjugated polyene [C] is 0.1 to 6.0 mol% based on the total
of the structural units of [A], [B] and [C] as 100 mol%;
(3) a Mooney viscosity ML!1+ 4)125°C at 125°C is 5 to 100; and
15 (4) a B value represented by the following formula (i) is
1.20 or more:
B value I [EX] + 2 [Y]) I [2 X [E] X I [X] + [Y]) I ---
I i ) ,
wherein [E], [X] and [Y] represent a mole fraction
20 of the ethylene [A], the C4-C20 a-olefin [B] and the non-conjugated
polyene [C] respectively, and [EX] represents an ethylene
[A] -C4-C20 a-olefin [B] diad chain fraction.
2. The ethylene·a-olefin·non-conjugated polyene copolymer
!!
'I
I
I
i
' i
I
I
!
i
i
SF-2890 456
according to claim 1, wherein the CrC20 a-olefin [B] is !-butene.
3. The ethylene·a-olefin·non-conjugated polyene copolymer
according to claim 1 or 2, wherein the
5 ethylene·a-olefin·non-conjugated polyene copolymer is obtained
by copolymerizing an ethylene, a C4-C20 a-olefin and a
non-conjugated polyene in the presence of an olefin
polymerization catalyst containing:
I a I a transition metal compound represented by.the
10 following general formula (VII] :
[VII]
wherein M is a titanium atom, a zirconium atom, or
a hafnium atom;
R5 and R6 are substituted aryl groups wherein one or
15 more of the hydrogen atoms of an aryl group are substituted with
an electron-donating substituent having a substituent constant
SF-2890 457
a of -0.2 or less in the Hammett's rule; wherein when the
substituted aryl group has a plurality of the electron-donating
substituents, each of the electron-donating substituents may be
the same or different; wherein the substituted aryl group
5 optionally comprises a substituent selected from C1-C20
hydrocarbon groups, silicon-containing groups,
nitrogen-containing groups, oxygen-containing groups, halogen
atoms and halogen-containing groups other than the
electron-donating substituents; and wherein when the substituted
10 aryl group comprises a plurality of the substituents, each of the
substituents may be the same or different;
Q is selected in an identical or different combination
from halogen atoms, C1-C20 hydrocarbon groups, anionic ligands,
and neutral ligands capable of being coordinated with a lone
15 electron pair; and
20
j is an integer of 1 to 4; and
(b) at least one compound selected from
(b-1) organometallic compounds,
(b-2) organoaluminum oxy-compounds, and
(b-3) components which react with the transition
metal compound (a) to form an ion pair.
4. A cross-linked ethylene·a-olefin·non-conjugated polyene
copolymer, wherein the ethylene ·a-olefin ·non-conjugated polyene
SF-2890 458
copolymer according to any one of claims 1 to 3 is cross-linked
using a cross-linking agent.
5. A molded article formed using the
5 ethylene ·ex-olefin ·non-conjugated polyene copolymer according to
any one of claims 1 to 3 or the cross-linked
ethylene ·0'-olefin ·non-conjugated polyene copolymer according to
claim 4.
;•.:·
10 6. A composition comprising the
i !i
ethylene ·ex-olefin ·non-conjugated polyene copolymer according to
' any one of claims 1 to 3.
7 • A method for manufacturing the
15 ethylene ·a-olefin ·non-conjugated polyene copolymer according to
any one of claims 1 to 3, wher~in the et;hylene, the C4-C20 a-ol~fin
and the non-conjugated polyene are copolymerized in the presence
of an olefin polymerization catalyst including:
(a) a transition metal compound represented by the
20 following general formula [VII]:
!
' -:
:
i
'i
:1
:]
:,,f
::
\i
SF-2890 459
Re
R' M<1j
., , [VII]
wherein M is a_ titanium atom, a zirconium atom, or
a hafnium atom;
R5 and R6 are substituted aryl groups wherein one or
5 more of the hydrogen atoms of an aryl group are substituted with
an electron-donating substituent having a substituent constant
a of -0.2 or less in the Hammett's rule; wherein when the
substituted aryl group has a plurality of the electron-donating
substituents, each of the electron-donating substituents may be
10 the same or different;, whe_rein _the --~3Ubsti.tute_d aryl group.
optionally contains a substituent selected from C1 -C20 hydrOcarbongroups,
silicon-containing groups, nitrogen-containing groups,
oxygen-containing groups, halogen atoms and halogen-containing
groups other than the electron-donating substituents; and wherein
15 when the substituted aryl group has a plurality of the substi tuents,
each of the substituents may be the same or different;
Q is selected in an identical or different combination
from halogen atoms, C1-C20 hydrocarbon groups, anionic ligands and
~
i:
fj
il
"II !
II
i
"
::
~
r"
' I'
~ I
I.I,
,[,:
[!
I'
'f.
h
ll
p
,,
:"j
':
SF-2890 460
neutral ligands capable of being coordinated with a lone electron
pair; and
j is an integer of 1 to 4; and
{b) at least one compound selected from
5 (b-1) organometallic compounds,
(b-2) organoaluminum oxy compounds, and
(b-3) components which react with the transition
metal· compound Ca) to form an ion pair.·
10 8. A composition for a seal packing, wherein the composition
comprises the ethylene·a-olefin·non-conjugated polyene
copolymer according to any one of claims 1 to 3.
9. A seal packing formed using the composition for a seal
15 packing according to claim 8.
10. The seal packing according to claim 9, wherein the seal
packing is a seal component for automobiles, a seal component for
machinery, a seal component for electronic and electrical
20 components, a gasket for construction, or a seal component for
civil engineering and building materials.
11. A composition comprising:
an ethylene ·a-olefin·non-conjugated polyene copolymer (1); and
an ethylene·a-olefin·non-conjugated polyene copolymer (2)
comprising a structural unit derived from ethylene [A'], a
structural unit derived from a C3-C20 a-olefin [B'] and a structural
unit derived from a non-conjugated polyene [C'}, and satisfying
5 the following I I ) :
I I) the B value represented by the following equation (i)
is less than 1. 20:
B value ~ ([EX]+ 2[Y]) I (2 X [E] X ([X]+ (Y])} ---
I i l
10 wherein [E] 1 [X] and [Y] represent a mole fraction
of the ethylene [A'], the C3-C20 a-olefin [B'] and the
non-conjugated polyene [C 1 ] respectively, and [EX] represents an
ethylene [A']-C3-C20 a-olefin [B'] diad chain fraction;
wherein the ethylene·a-olefin·non-conjugated polyene
15 copolymer (1) is the ethylene·a-olefin·non-conjugated polyene
copolymer of any one of claims 1 to 3.
12. The composition according to claim 11, wherein a mass ratio
[(1)/{2)] of the ethylene·a-olefin·non-conjugated polyene
20 copolymer {1) to the ethylene·a-olefin·non-conjugated polyene
copolymer (2} is 10/90 to 50/50.
13. A cross-linked material obtained by cross-linking the
composition according to claim 11 or 12.
A cross-linked foam obtained by cross-linking and foaming
the composition according to claim 11 or 12.
5 15. A sound insulation material obtained from the composition
according to claim 11-or 12.
16. A composition for forming a hose, wherein the composition
comprises the ethylene·a-olefin·non-conjugated polyene.
10 copolymer according to any one of claims 1 to 3.
17. A hose having a layer formed by cross-linking t-reatment of
the composition according to claim 16 for forming a hose.
'r 15 18. The hose according to claim 17, wherein the hose is used
for any of uses for automobiles, motorbikes, industrial machi:nery,
construction machinery or agricultural machinery.
19. A method for manufacturing an
20 ethylene/a-olefin/non-conjugated polyene copolymer, the method
comprising copolymerizing an ethylene, an a-olefin having three
or more carbon atoms and a non-conjugated polyene in the presence
of an olefin polymerization catalyst containing:
(a) a transition metal compound represented by the
following general formula [ I ] :
MQ_;
wherein Y is selected from a carbon atom, a silicon
atom, a germanium atom and a tin atom;
M is a titanium atom, a zirconium atom or a hafnium
atom;
R1
, R2
, R3
, R4
, R5 and R6
, each of which may be the _same
or different, are atoms or substituents selected from hydrogen
atoms, C1-C20 hydrocarbon groups, aryl groups, substituted aryl
groups, silicon-containing groups, nitrogen-containing groups,
oxygen-containing groups, halogen atoms and halogen-containing
groups;
adjacent substituents between R1 and R6 are optionally
bound together to form a ring;
Q is selected in an identical or different combination
from halogen atoms, C1-C20 hydrocarbon groups, anionic ligands and
neutral ligands capable of being coordinated with a lone electron
pair;
(b)
n is an integer of 1 to 4; and
j is an integer of 1 to 4; and
at least one compound selected from
(b-1) organometallic compounds,
(b-2) organoaluminum oxy-compounds, and
(b-3) components which react with the transition
10 metal compound (a) to form an ion pair.
20. The method for manufacturing an
ethylene/ex-olefin/non-conjugated polyene copolymer according to
claim 19, wherein n in the general formula [I] is 1.
21. The method for manufacturing an
ethylene/a-olefin/non-conjugated polyene copolymer according to
claim 19 or 20, wherein R1
, R2
, R3 and R4 in the general formula
[I] are all hydrogen atoms.
22. The method for manufacturing an
ethylene/ex-olefin/non-conjugated polyene copolymer according to
any one of claims 19 to 21, wherein Y in the general formula [I]
is a carbon atom.
23. The method for manufacturing an
ethylene/a-olefin/non-conjugated polyene copolymer according to
any one of claims 19 to 22, wherein R5 and R6 in the general formula
[I] are groups selected from aryl groups and substituted aryl
groups.
24. The method for manufacturing an
ethylene/a-olefin/non-conjugated polyene copolymer according to
~·. 10 claim 23, wherein R5 and R6 in the general formula [I] are
substituted aryl groups wherein one or more of the hydrogen atoms
of an aryl group are substituted with an electron-donating
substituent having a substituent constant a of -0.2 or less in
the Hammett's rule; wherein when the substituted aryl group has
15 a plurality of the electron-donating substituents, each of the
electron~donating substituents may be the same_ or different;
wherein the substituted aryl groups optionally contain a
substituent selected from C1-C20 hydrocarbon groups,
silicon-containing groups, nitrogen-containing groups,
20 oxygen-containing groups, halogen atoms and halogen-containing
groups other than the electron-donating substituents; and wherein
when the substituted aryl group has a plurality of the substituents,
each of the substituents may be the same or different.
25. The method for manufacturing an
ethylene/a-olefin/non-conjugated polyene copolymer according to
claim 24, wherein the electron-donating substituent is a group
selected from nitrogen-containing groups and oxygen-containing
5 groups.
26. The method for manufacturing an
ethylene/a.:...olefin/non-conjugated polyene copolymer according to
claim 25, wherein R5 and R6 in the general formula [I] are
10 substituted phenyl groups in which a group selected from the
nitrogen-containing groups and the oxygen-containing groups is
contained in the meta position and/or para position to the bond
toY.
15 27. The method for manufacturing an
ethylene/a-olefin/n