U.S. patent application number 09/737963 was filed with the patent office on 2001-10-11 for olefin copolymer having functional group, production process thereof and rubber composition.
This patent application is currently assigned to JSR Corporation. Invention is credited to Maruyama, Youichirou, Oshima, Noboru, Sawada, Katsutoshi, Tsuji, Syouei.
Application Number | 20010029288 09/737963 |
Document ID | / |
Family ID | 18499210 |
Filed Date | 2001-10-11 |
United States Patent
Application |
20010029288 |
Kind Code |
A1 |
Oshima, Noboru ; et
al. |
October 11, 2001 |
Olefin copolymer having functional group, production process
thereof and rubber composition
Abstract
Disclosed herein are an olefin copolymer having a functional
group, which comprises a structural unit (a) derived from ethylene,
a structural unit (b) derived from an .alpha.-olefin having 3 to 12
carbon atoms, and a structural unit (c) represented by the
following general formula (1), and has an intrinsic viscosity
.vertline..eta..vertline. of 0.1 to 10 dl/g as measured in decalin
at 135.degree. C., a production process thereof and a rubber
composition containing the copolymer; General formula (1): 1
wherein X.sup.1 and X.sup.2 mean, independently of each other, a
hydrogen atom, a hydrocarbon group or the following specific
functional group, at least one of X.sup.1 and X.sup.2 is the
specific functional group, R.sup.1 and R.sup.2 denote,
independently of each other, a hydrogen atom or a hydrocarbon group
having 1 to 10 carbon atoms, one of R.sup.1 and R.sup.2, which is
bonded to a carbon atom to which the specific functional group is
bonded, is the hydrocarbon group having 1 to 10 carbon atoms, and n
stands for an integer of 0 to 2; Specific functional group: a
functional group selected from the group consisting of a hydroxyl
group, a hydrocarbon group to which a hydroxyl group is bonded, a
carboxyl group, a hydrocarbon group to which a carboxyl group is
bonded, a primary or secondary amino group, a hydrocarbon group to
which a primary or secondary amino group is bonded, a quaternary
ammonium salt of a primary or secondary amino group and a
hydrocarbon group to which a primary or secondary amino group is
bonded, an amide group having at least one active hydrogen atom
bonded to a nitrogen atom, a hydrocarbon group to which such a
amide group is bonded, and an imide group composed of X.sup.1 and
X.sup.2 and represented by --CO--NH--CO--.
Inventors: |
Oshima, Noboru; (Tokyo,
JP) ; Maruyama, Youichirou; (Tokyo, JP) ;
Sawada, Katsutoshi; (Tokyo, JP) ; Tsuji, Syouei;
(Tokyo, JP) |
Correspondence
Address: |
OBLON SPIVAK MCCLELLAND MAIER & NEUSTADT PC
FOURTH FLOOR
1755 JEFFERSON DAVIS HIGHWAY
ARLINGTON
VA
22202
US
|
Assignee: |
JSR Corporation
Tokyo
JP
|
Family ID: |
18499210 |
Appl. No.: |
09/737963 |
Filed: |
December 18, 2000 |
Current U.S.
Class: |
526/282 ;
525/326.1 |
Current CPC
Class: |
C08L 23/16 20130101;
C08F 210/18 20130101; C08L 23/02 20130101; C08F 210/02 20130101;
C08F 210/16 20130101; C08F 210/16 20130101; C08F 210/18 20130101;
C08F 210/02 20130101; C08F 210/18 20130101; C08L 23/02 20130101;
C08F 210/18 20130101; C08F 2500/25 20130101; C08F 2500/21 20130101;
C08F 236/20 20130101; C08L 2666/04 20130101; C08F 2500/17 20130101;
C08F 4/68 20130101; C08F 232/08 20130101; C08F 2500/17 20130101;
C08F 210/06 20130101; C08F 210/06 20130101; C08F 2500/25 20130101;
C08F 210/06 20130101; C08F 2500/17 20130101; C08F 232/08 20130101;
C08F 2500/17 20130101; C08F 232/08 20130101; C08F 236/20 20130101;
C08F 232/08 20130101; C08F 2500/21 20130101; C08F 2500/25 20130101;
C08F 2500/21 20130101 |
Class at
Publication: |
526/282 ;
525/326.1 |
International
Class: |
C08F 036/00 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 27, 1999 |
JP |
11-371731 |
Claims
What is claimed is:
1. An olefin copolymer having a functional group, which comprises:
a structural unit (a) derived from ethylene, a structural unit (b)
derived from an .alpha.-olefin having 3 to 12 carbon atoms, and a
structural unit (c) represented by the following general formula
(1), and has an intrinsic viscosity [.eta.] of 0.1 to 10 dl/g as
measured in decalin at 135.degree. C.; General formula (1):
4wherein X.sup.1 and X.sup.2 mean, independently of each other, a
hydrogen atom, a hydrocarbon group or the following specific
functional group, at least one of X.sup.1 and X.sup.2 is the
specific functional group, R.sup.1 and R.sup.2 denote,
independently of each other, a hydrogen atom or a hydrocarbon group
having 1 to 10 carbon atoms, one of R.sup.1 and R.sup.2, which is
bonded to a carbon atom to which the specific functional group is
bonded, is the hydrocarbon group having 1 to 10 carbon atoms, and n
stands for an integer of 0 to 2; Specific functional group: a
functional group selected from the group consisting of a hydroxyl
group, a hydrocarbon group to which a hydroxyl group is bonded, a
carboxyl group, a hydrocarbon group to which a carboxyl group is
bonded, a primary or secondary amino group, a hydrocarbon group to
which a primary or secondary amino group is bonded, a quaternary
ammonium salt of a primary or secondary amino group and a
hydrocarbon group to which a primary or secondary amino group is
bonded, an amide group having at least one active hydrogen atom
bonded to a nitrogen atom, a hydrocarbon group to which such a
amide group is bonded, and an imide group composed of X.sup.1 and
X.sup.2 and represented by --CO--NH--CO--.
2. An olefin copolymer having a functional group, which comprises:
a structural unit (a) derived from ethylene, a structural unit (b)
derived from an .alpha.-olefin having 3 to 12 carbon atoms, a
structural unit (c) represented by the general formula (1) set
forth in claim 1, and a structural unit (d) derived from a
nonconjugated diene, and has an intrinsic viscosity [.eta.] of 0.1
to 10 dl/g as measured in decalin at 135.degree. C.
3. The olefin copolymer having the functional group according to
claim 1 or 2, wherein the structural unit (a) derived from ethylene
is 5 to 90 mol %, the structural unit (b) derived from the
.alpha.-olefin having 3 to 12 carbon atoms is 5 to 60 mol %, the
structural unit (c) represented by the general formula (1) is 0.01
to 30 mol %, and the structural unit (d) derived from a
nonconjugated diene is 0 to 12 mol %.
4. The olefin copolymer having the functional group according to
any one of claims 1 to 3, wherein the structural unit (c)
represented by the general formula (1) is such that only one of
X.sup.1 and X.sup.2 in the general formula (1) is the specific
functional group, and R.sup.1 or R.sup.2 which is bonded to the
carbon atom to which the specific functional group is bonded, is a
hydrocarbon group having 1 or 2 carbon atoms.
5. The olefin copolymer having the functional group according to
any one of claims 1 to 3, wherein the structural unit (c)
represented by the general formula (1) is such that only one of
X.sup.1 and X.sup.2 in the general formula (1) is the specific
functional group, and R.sup.1 or R.sup.2, which is bonded to the
carbon atom to which the specific functional group is bonded, is a
hydrocarbon group having 1 or 2 carbon atoms, the other of X.sup.1
and X.sup.2 is a hydrogen atom, and R.sup.1 or R.sup.2, which is
bonded to the carbon atom to which the hydrogen atom is bonded, is
a hydrogen atom.
6. The olefin copolymer having the functional group according to
any one of claims 1 to 3, wherein the glass transition temperature
is -90 to 50.degree. C.
7. A process for producing an olefin copolymer having a functional
group, which comprises the steps of: reacting a functional
group-containing cycloolefin represented by the following general
formula (2) with an organometallic compound comprising a metal
selected from metals of Groups 2, 12 and 13 of the periodic table,
and polymerizing the resulting reaction product with ethylene, an
.alpha.-olefin having 3 to 12 carbon atoms and a nonconjugated
diene optionally used in the presence of a catalyst composed of a
transition metal compound and an organoaluminum compound; General
formula (2): 5wherein X.sup.1 and X.sup.2 mean, independently of
each other, a hydrogen atom, a hydrocarbon group or the following
specific functional group, at least one of X.sup.1 and X.sup.2 is
the specific functional group, R.sup.1 and R.sup.2 denote,
independently of each other, a hydrogen atom or a hydrocarbon group
having 1 to 10 carbon atoms, one of R.sup.1 and R.sup.2, which is
bonded to a carbon atom to which the specific functional group is
bonded, is the hydrocarbon group having 1 to 10 carbon atoms, and n
stands for an integer of 0 to 2; Specific functional group: a
functional group selected from the group consisting of a hydroxyl
group, a hydrocarbon group to which a hydroxyl group is bonded, a
carboxyl group, a hydrocarbon group to which a carboxyl group is
bonded, a primary or secondary amino group, a hydrocarbon group to
which a primary or secondary amino group is bonded, a quaternary
ammonium salt of a primary or secondary amino group and a
hydrocarbon group to which a primary or secondary amino group is
bonded, an amide group having at least one active hydrogen atom
bonded to a nitrogen atom, a hydrocarbon group to which such a
amide group is bonded, and an imide group composed of X.sup.1 and
X.sup.2 and represented by --CO--NH--CO--.
8. The process according to claim 7, wherein the organometallic
compound comprising the metal selected from metals of Groups 2, 12
and 13 of the periodic table is an organoaluminum compound.
9. The process according to claim 7 or 8, wherein the
organometallic compound comprising the metal selected from metals
of Groups 2, 12 and 13 of the periodic table is used in a
proportion of at least 0.8 equivalents per equivalent of the
functional group in the functional group-containing cycloolefin
represented by the general formula (2).
10. A rubber composition comprising: (A) the olefin copolymer
having the functional group according any one of claims 1 to 6, and
(B) a vulcanizing agent and/or a crosslinking agent.
11. The rubber composition according to claim 10, which comprises
(C) an olefin copolymer having no functional group.
12. The rubber composition according to claim 11, wherein (C) the
olefin copolymer having no functional group is a copolymer
comprising a structural unit derived from ethylene and a structural
unit derived from an .alpha.-olefin having 3 to 12 carbon atoms,
and/or a copolymer comprising a structural unit derived from
ethylene, a structural unit derived from an .alpha.-olefin having 3
to 12 carbon atoms and a structural unit derived from a
nonconjugated diene.
13. The rubber composition according to claim 11 or 12, wherein a
ratio of (A) the olefin copolymer having the functional group
according to any one of claims 1 to 4 to (C) the olefin copolymer
having no functional group is 1:99 to 99:1 in terms of a weight
ratio.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to an olefin copolymer having
a functional group, a production process thereof and a rubber
composition comprising the olefin copolymer having the functional
group, and more particularly to an olefin copolymer having a
functional group, which permits providing an elastomer excellent in
adhesion to and compatibility with other materials, coating
property, printability and durability, and suitable for use as a
material for automotive parts, mechanical parts, electronic parts,
civil engineering and construction materials, etc., a production
process thereof, and a rubber composition comprising the olefin
copolymer having the functional group.
[0003] 2. Description of the Background Art
[0004] Olefin copolymer elastomers such as ethylene/.alpha.-olefin
copolymer elastomers and ethylene/.alpha.-olefin/nonconjugated
diene copolymer elastomers have heretofore been widely used as
materials for automotive parts, mechanical parts, civil engineering
and construction materials, etc. because they are elastomeric
materials excellent in heat resistance and weather resistance. The
olefin copolymer elastomers are also widely used as modifiers for
resins such as polypropylene and polyethylene.
[0005] However, such olefin copolymer elastomers involve problems
that they have neither polar group nor functional group in their
molecular structures, and so their adhesion to metals, and adhesion
to and compatibility with other elastomers and resins than
polyolefins are low, and the resulting molded or formed products
are inferior in coating property and printability.
[0006] For such reasons, olefin copolymers with a functional group
such as a carboxyl group or amino group introduced by using a
cycloolefin having such a functional group as a monomer component
have been proposed (see Japanese Patent Publication No. 43275/1974,
Japanese Patent Application Laid-Open Nos. 259012/1989 and
54009/1989, Japanese Patent Application Laid-Open No. 503963/1992
(through PCT route), etc.).
[0007] However, such olefin copolymers with the functional group
introduced thereinto have the following problems.
[0008] Namely, an active tertiary hydrogen atom (hydrogen atom
bonded to a tertiary carbon atom) produced by substitution of a
hydrogen atom with the functional group is present in a structural
unit derived from the cycloolefin having the functional group, in
other words, the tertiary hydrogen atom is bonded to a carbon atom
to which the functional group has been bonded. When such a tertiary
hydrogen atom is present in the copolymer, the tertiary hydrogen
atom tends to separate from the carbon atom to produce a radical.
Therefore, such a copolymer is apt to cause scission of a molecular
chain, deterioration by oxidation and deterioration by the
separation of a substituent group containing the functional group
due to the formation of the radical. Accordingly, it is difficult
to provide an elastomer excellent in durability by the olefin
copolymer in which the functional group has been introduced.
[0009] In addition, a cycloolefin having, for example, a carboxyl
group as a functional group gives off a strong odor. When such a
cycloolefin is used as a monomer, the resulting copolymer also
gives off a strong odor because the cycloolefin unavoidably remains
in the copolymer. Therefore, such a copolymer involves an
environmental or sanitary problem.
SUMMARY OF THE INVENTION
[0010] The present invention has been made on the basis of the
foregoing circumstances, and it is the first object of the present
invention to provide an olefin copolymer having a functional group,
which permits providing an elastomer which is high in adhesion to
and compatibility with other materials, coating property and
printability and excellent in durability, and gives off no or
little odor.
[0011] The second object of the present invention is to provide a
process capable of exactly producing an olefin copolymer having a
functional group, which permits providing an elastomer which is
high in adhesion to and compatibility with other materials, coating
property and printability and excellent in durability, and gives
off no or little odor.
[0012] The third object of the present invention is to provide a
rubber composition, which permits providing an elastomer which is
high in adhesion to and compatibility with other materials, coating
property and printability and excellent in durability, mechanical
properties and abrasion resistance, and gives off no or little
odor.
[0013] According to the present invention, there is thus provided
an olefin copolymer having a functional group, which comprises:
[0014] a structural unit (a) derived from ethylene,
[0015] a structural unit (b) derived from an .alpha.-olefin having
3 to 12 carbon atoms, and
[0016] a structural unit (c) represented by the following general
formula (1),
[0017] and has an intrinsic viscosity [.eta.] of 0.1 to 10 dl/g as
measured in decalin at 135.degree. C.;
[0018] General formula (1): 2
[0019] wherein X.sup.1 and X.sup.2 mean, independently of each
other, a hydrogen atom, a hydrocarbon group or the following
specific functional group, at least one of X.sup.1 and X.sup.2 is
the specific functional group, R.sup.1 and R.sup.2 denote,
independently of each other, a hydrogen atom or a hydrocarbon group
having 1 to 10 carbon atoms, one of R.sup.1 and R.sup.2, which is
bonded to a carbon atom to which the specific functional group is
bonded, is the hydrocarbon group having 1 to 10 carbon atoms, and n
stands for an integer of 0 to 2;
[0020] Specific functional group:
[0021] a functional group selected from the group consisting of a
hydroxyl group, a hydrocarbon group to which a hydroxyl group is
bonded, a carboxyl group, a hydrocarbon group to which a carboxyl
group is bonded, a primary or secondary amino group, a hydrocarbon
group to which a primary or secondary amino group is bonded, a
quaternary ammonium salt of a primary or secondary amino group and
a hydrocarbon group to which a primary or secondary amino group is
bonded, an amide group having at least one active hydrogen atom
bonded to a nitrogen atom, a hydrocarbon group to which such a
amide group is bonded, and an imide group composed of X.sup.1 and
X.sup.2 and represented by --CO--NH--CO--.
[0022] According to the present invention, there is also provided
an olefin copolymer having a functional group, which comprises:
[0023] a structural unit (a) derived from ethylene,
[0024] a structural unit (b) derived from an .alpha.-olefin having
3 to 12 carbon atoms,
[0025] a structural unit (c) represented by the above-described
general formula (1), and
[0026] a structural unit (d) derived from a nonconjugated
diene,
[0027] and has an intrinsic viscosity [.eta.] of 0.1 to 10 dl/g as
measured in decalin at 135.degree. C.
[0028] In the olefin copolymers having the functional group
according to the present invention, it may be preferable that
proportion of the structural unit (a) derived from ethylene be 5 to
90 mol %, the structural unit (b) derived from the .alpha.-olefin
having 3 to 12 carbon atoms be 5 to 60 mol %, the structural unit
(c) represented by the general formula (1) be 0.01 to 30 mol %, and
the structural unit (d) derived from a nonconjugated diene be 0 to
12 mol %.
[0029] In the olefin copolymers having the functional group
according to the present invention, the structural unit (c)
represented by the general formula (1) may preferably be such that
only one of X.sup.1 and X.sup.2 in the general formula (1) is the
specific functional group, and R.sup.1 or R.sup.2, which is bonded
to the carbon atom to which the specific functional group is
bonded, is a hydrocarbon group having 1 or 2 carbon atoms, and
particularly that the other of X.sup.1 and X.sup.2 is a hydrogen
atom, and R.sup.1 or R.sup.2, which is bonded to the carbon atom to
which the hydrogen atom is bonded, is a hydrogen atom.
[0030] In the olefin copolymers having the functional group
according to the present invention, the glass transition
temperature may preferably be -90 to 50.degree. C., more preferably
-70 to 10.degree. C.
[0031] According to the present invention, there is further
provided a process for producing an olefin copolymer having a
functional group, which comprises the steps of:
[0032] reacting a functional group-containing cycloolefin
represented by the following general formula (2) with an
organometallic compound comprising a metal selected from metals of
Groups 2, 12 and 13 of the periodic table, and
[0033] polymerizing the resulting reaction product with ethylene,
an .alpha.-olefin having 3 to 12 carbon atoms and a nonconjugated
diene optionally used in the presence of a catalyst composed of a
transition metal compound and an organoaluminum compound;
[0034] General formula (2): 3
[0035] wherein X.sup.1 and X.sup.2 mean, independently of each
other, a hydrogen atom, a hydrocarbon group or the following
specific functional group, at least one of X.sup.1 and X.sup.2 is
the specific functional group, R.sup.1 and R.sup.2 denote,
independently of each other, a hydrogen atom or a hydrocarbon group
having 1 to 10 carbon atoms, one of R.sup.1 and R.sup.2, which is
bonded to a carbon atom to which the specific functional group is
bonded, is the hydrocarbon group having 1 to 10 carbon atoms, and n
stands for an integer of 0 to 2;
[0036] Specific functional group:
[0037] a functional group selected from the group consisting of a
hydroxyl group, a hydrocarbon group to which a hydroxyl group is
bonded, a carboxyl group, a hydrocarbon group to which a carboxyl
group is bonded, a primary or secondary amino group, a hydrocarbon
group to which a primary or secondary amino group is bonded, a
quaternary ammonium salt of a primary or secondary amino group and
a hydrocarbon group to which a primary or secondary amino group is
bonded, an amide group having at least one active hydrogen atom
bonded to a nitrogen atom, a hydrocarbon group to which such a
amide group is bonded, and an imide group composed of X.sup.1 and
X.sup.2 and represented by --CO--NH--CO--.
[0038] In the process for producing the olefin copolymer having the
functional group according to the present invention, the
organometallic compound comprising the metal selected from metals
of Groups 2, 12 and 13 of the periodic table may preferably be an
organoaluminum compound.
[0039] The organometallic compound comprising the metal selected
from metals of Groups 2, 12 and 13 of the periodic table may
preferably be used in a proportion of at least 0.8 equivalents per
equivalent of the functional group in the functional
group-containing cycloolefin represented by the general formula
(2).
[0040] According to the present invention, there is still further
provided a rubber composition comprising:
[0041] (A) the olefin copolymer having the functional group
described above, and
[0042] (B) a vulcanizing agent and/or a crosslinking agent.
[0043] The rubber composition according to the present invention
may comprise (C) an olefin copolymer having no functional
group.
[0044] In such a rubber composition, (C) the olefin copolymer
having no functional group may preferably be a copolymer comprising
a structural unit derived from ethylene and a structural unit
derived from an (.alpha.-olefin having 3 to 12 carbon atoms, and/or
a copolymer comprising a structural unit derived from ethylene, a
structural unit derived from an .alpha.-olefin having 3 to 12
carbon atoms and a structural unit derived from a nonconjugated
diene.
[0045] A ratio of (A) the olefin copolymer having the functional
group described above to (C) the olefin copolymer having no
functional group may preferably be 1:99 to 99:1 in terms of a
weight ratio.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0046] The embodiments of the present invention will hereinafter be
described in detail.
[0047] The olefin copolymer having the functional group
(hereinafter also referred to as "the functional group-containing
olefin copolymer") according to the present invention comprises a
structural unit (a) (hereinafter also referred to as "the
structural unit (a)" merely) derived from ethylene, a structural
unit (b) (hereinafter also referred to as "the structural unit (b)"
merely) derived from an .alpha.-olefin (hereinafter also referred
to as "the specific .alpha.-olefin") having 3 to 12 carbon atoms
and a structural unit (c) (hereinafter also referred to as "the
structural unit (c)" merely) represented by the above-described
general formula (1), and optionally a structural unit (d)
(hereinafter also referred to as "the structural unit (d)" merely)
derived from a nonconjugated diene.
[0048] In the functional group-containing olefin copolymer
according to the present invention, the structural unit (a) is
preferably contained in a range of 5 to 90 mol %, more preferably
10 to 85 mol %, particularly preferably 15 to 80 mol % based on the
whole structural unit.
[0049] When the proportion of the structural unit (a) contained is
5 mol % or higher, a functional group-containing cycloolefin
represented by the general formula (2), which will be described
subsequently, can be easily copolymerized therewith, and moreover
the resulting copolymer tends to provide an elastomer having
excellent durability. When the proportion of the structural unit
(a) is 90 mol % or lower on the other hand, a copolymer exhibiting
the behavior as an elastomer is provided with ease.
[0050] The specific .alpha.-olefin used for forming the structural
unit (b) is an .alpha.-olefin having 3 to 12 carbon atoms, and
specific examples thereof include propylene, 1-butene, 1-pentene,
4-methylpentene-1, 1-hexene, 1-heptene, 1-octene, 1-decene,
1-dodecene, styrene and p-methylstyrene. These compounds may be
used either singly or in any combination thereof.
[0051] When the .alpha.-olefin having at most 12 carbon atoms is
used, the copolymerizability of such an .alpha.-olefin with other
monomers is easy to become satisfactory.
[0052] The structural unit (b) is preferably contained in a range
of 5 to 60 mol %, more preferably 10 to 55 mol %, particularly
preferably 15 to 50 mol % based on the whole structural unit.
[0053] When the proportion of the structural unit (b) contained is
5 mol % or higher, the resulting copolymer tends to provide an
elastomer having sufficient elasticity. When the proportion of the
structural unit (b) is 60 mol % or lower on the other hand, an
elastomer obtained from the resulting copolymer tends to have good
durability.
[0054] The structural unit (c) is a structural unit represented by
the general formula (1) and formed by the functional
group-containing cycloolefin (hereinafter also referred to as "the
specific functional group-containing cycloolefin") represented by
the general formula (2).
[0055] In the general formulae (1) and (2), groups X.sup.1 and
X.sup.2 mean, independently of each other, a hydrogen atom, a
hydrocarbon group or a specific functional group, and at least one
of X.sup.1 and X.sup.2 is the specific functional group.
[0056] The specific functional group is a functional group selected
from the group consisting of a hydroxyl group, a hydrocarbon group
to which a hydroxyl group is bonded, a carboxyl group, a
hydrocarbon group to which a carboxyl group is bonded, a primary
amino group and a secondary amino group, a hydrocarbon group to
which a primary or secondary amino group is bonded, a quaternary
ammonium salt of a primary or secondary amino group or of a
hydrocarbon group to which a primary or secondary amino group is
bonded, an amide group having at least one active hydrogen atom
bonded to a nitrogen atom, a hydrocarbon group to which such an
amide group is bonded, and an imide group composed of X.sup.1 and
X.sup.2 and represented by --CO--NH--CO--. In the hydrocarbon
groups to which the hydroxyl group is bonded, the hydrocarbon
groups to which the carboxyl group is bonded, and the hydrocarbon
groups to which the amino group is bonded, or the quaternary
ammonium salts thereof, the number of carbon atoms is preferably 1
to 5, excluding those of substituent groups thereof.
[0057] R.sup.1 and R.sup.2 denote, independently of each other, a
hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms,
and one of R.sup.1 and R.sup.2, which is bonded to a carbon atom to
which the specific functional group is bonded, is the hydrocarbon
group having 1 to 10 carbon atoms.
[0058] The value of the number n of repeated structural units is an
integer of 0 to 2.
[0059] The structural unit (c) is preferably such that only one of
groups X1 and X.sup.2 in the general formula (1) is the specific
functional group, and the group R.sup.1 or R.sup.2, which is bonded
to the carbon atom to which the specific functional group is
bonded, is a hydrocarbon group having 1 or 2 carbon atoms, in that
the decomposition of the resulting copolymer is hard to occur, and
an elastomer having excellent durability is provided. In
particular, the structural unit (c) is preferably such that that
the other of the groups X.sup.1 and X.sup.2 is a hydrogen atom, and
the group R.sup.1 or R.sup.2, which is bonded to the carbon atom to
which the hydrogen atom is bonded, is a hydrogen atom.
[0060] The specific functional group is preferably --COOH (carboxyl
group), --NH.sub.2 (amino group), --NHCH.sub.3 (aminomethyl group),
--CONH.sub.2 or --CONR.sup.3H (in which R.sup.3 means an alkyl
group). Of these groups, --COOH (carboxyl group), --CONH.sub.2 or
--CONR.sup.3H is more preferred.
[0061] If the number of repeated structural units n in the general
formula (2) is 3 or more, it is difficult to copolymerize such a
functional group-containing cycloolefin with other monomers.
[0062] The specific functional group-containing cycloolefin used
for forming the structural unit (c) is prepared by condensing
cyclopentadiene with a functional group-containing olefin by the
Diels-Alder reaction and optionally subjecting the reaction product
to a hydrolytic reaction.
[0063] Specific examples of such a specific functional
group-containing cycloolefin include:
[0064] 5,6-dimethyl-5,6-dihydroxy-bicyclo[2. 2. 1]-2-heptene,
[0065] 5,6-dimethyl-5,6-dicarboxy-bicyclo[2. 2. 1]-2-heptene,
[0066] 5,6-diethyl-5,6-dicarboxy-bicyclo[2. 2. 1]-2-heptene,
[0067] 5,6-dimethyl-5,6-bis(carboxymethyl)-bicyclo-[2. 2.
1]-2-heptene,
[0068] 5,6-diethyl-5,6-bis(carboxymethyl)-bicyclo-[2. 2.
1]-2-heptene,
[0069] 5,6-dimethyl-5,6-bis(hydroxymethyl)-bicyclo-[2. 2.
1]-2-heptene,
[0070] 5,6-diethyl-5,6-bis(hydroxymethyl)-bicyclo-[2. 2.
1]-2-heptene,
[0071] 5,6-dimethyl-5,6-bis(aminomethyl)-bicyclo[2. 2.
1]-2-heptene,
[0072] 5,6-diethyl-5,6-bis(aminomethyl)-bicyclo[2. 2.
1]-2-heptene,
[0073] 5,6-dimethyl-5,6-bis(aminopropyl)-bicyclo[2. 2.
1]-2-heptene,
[0074] 5,6-dimethyl-5,6-bis(aminocarbonyl)-bicyclo-[2. 2.
1]-2-heptene,
[0075] 5,6-dimethyl-5,6-bis(N-methyl-aminocarbonyl)-bicyclo[2. 2.
1]-2-heptene,
[0076] 5,6-dimethyl-5,6-bis(N-propyl-aminocarbonyl)-bicyclo[2. 2.
1]-2-heptene,
[0077] 5,6-diethyl-5,6-bis(aminocarbonyl)-bicyclo-[2. 2.
1]-2-heptene,
[0078] 5,6-diethyl-5,6-bis(N-ethyl-aminocarbonyl)-bicyclo[2. 2.
1]-2-heptene,
[0079] 5,6-dimethyl-bicyclo[2. 2. 1]-2-heptene-5,6-dicarboxylic
acid imide,
[0080] 5-methyl-5-hydroxy-bicyclo[2. 2. 1]-2-heptene,
[0081] 5-methyl5-carboxy-bicyclo[2. 2. 1]-2-heptene,
[0082] 5-ethyl-5-carboxy-bicyclo[2. 2. 1]-2-heptene,
[0083] 5-methyl-5-hydroxymethyl-bicyclo[2. 2. 1]-2-heptene,
[0084] 5-ethyl-5-hydroxymethyl-bicyclo[2. 2. 1]-2-heptene,
[0085] 5-methyl-5-carboxymethyl-bicyclo[2. 2. 1]-2-heptene,
[0086] 5-ethyl-5-carboxymethyl-bicyclo[2. 2. 1]-2-heptene,
[0087] 5-methyl-5-aminomethyl-bicyclo[2. 2. 1]-2-heptene,
[0088] 5-ethyl-5-aminomethyl-bicyclo[2. 2. 1]-2-heptene,
[0089] 5-methyl-5-aminopropyl-bicyclo[2. 2. 1]-2-heptene,
[0090] 5-methyl-5-aminocarbonyl-bicyclo[2. 2. 1]-2-heptene,
[0091] 5-methyl-5-N-methyl-aminocarbonyl-bicyclo[2. 2.
1]-2-heptene,
[0092] 5-methyl-5-N-propyl-aminocarbonyl-bicyclo[2. 2.
1]-2-heptene,
[0093] 5-ethyl-5-aminocarbonyl-bicyclo[2. 2. 1]-2-heptene,
[0094] 5-ethyl-5-N-ethyl-aminocarbonyl-bicyclo[2. 2.
1]-2-heptene,
[0095] 8,9-dimethyl-8,9-dicarboxy-tetracyclo-[4. 4. 0.
1.sup.2,5.1.sup.7,10]-3-dodecene,
[0096] 8,9-diethyl-8,9-dicarboxy-tetracyclo-[4. 4. 0.
1.sup.2,5.1.sup.7,10]-3-dodecene,
[0097] 8,9-dimethyl-8,9-bis(hydroxymethyl)-tetracyclo-[4. 4. 0.
1.sup.2,5.1.sup.7,10]-3-dodecene,
[0098] 8,9-diethyl-8,9-bis(hydroxymethyl)-tetracyclo-[4. 4. 0.
1.sup.2,5.1.sup.7,10]-3-dodecene,
[0099] 8,9-dimethyl-8,9-bis(aminomethyl)-tetracyclo-[4. 4. 0.
1.sup.2,5.1.sup.7,10]-3-dodecene,
[0100] 8,9-diethyl-8,9-bis(aminomethyl)-tetracyclo-[4. 4. 0.
1.sup.2,5.1.sup.7,10]-3-dodecene,
[0101] 8,9-dimethyl-8,9-bis(aminocarbonyl)-tetracyclo-[4. 4. 0.
1.sup.2,5.1.sup.7,10]-3-dodecene,
[0102] 8,9-dimethyl-8,9-bis(N-methyl-aminocarbonyl)-tetracyclo[4.
4. 0. 1.sup.2,5.1.sup.7,10]-3-dodecene,
[0103] 8,9-diethyl-8,9-bis(aminocarbonyl)-tetracyclo-[4. 4. 0.
1.sup.2,5.1.sup.7,10]-3-dodecene,
[0104] 8,9-diethyl-8,9-bis(N-ethylaminocarbonyl)-tetracyclo[4. 4.
0. 1.sup.2,5.1.sup.7,10]-3-dodecene,
[0105] 8-methyl-8-carboxy-tetracyclo[4. 4. 0.
1.sup.2,5.1.sup.7,10]-3-dode- cene,
[0106] 8-ethyl-8-carboxy-tetracyclo[4. 4. 0.
1.sup.2,5.1.sup.7,10]-3-dodec- ene,
[0107] 8-methyl-8-hydroxymethyl-tetracyclo-[4. 4. 0.
1.sup.2,5.1.sup.7,10]-3-dodecene,
[0108] 8-ethyl-8-hydroxymethyl-tetracyclo-[4. 4. 0.
1.sup.2,5.1.sup.7,10]-3-dodecene,
[0109] 8-methyl-8-aminomethyl-tetracyclo-[4. 4. 0.
1.sup.2,5.1.sup.7,10]-3- -dodecene,
[0110] 8-ethyl-8-aminomethyl-tetracyclo[4. 4. 0.
1.sup.2,5.1.sup.7,10]-3-d- odecene,
[0111] 8-methyl-8-aminocarbonyl-tetracyclo-[4. 4. 0.
1.sup.2,5.1.sup.7,10]-3-dodecene,
[0112] 8-methyl-8-N-methyl-aminocarbonyl-tetracyclo-[4. 4. 0.
1.sup.2,5.1.sup.7,10]-3-dodecene,
[0113] 8-ethyl-8-aminocarbonyl-tetracyclo-[4. 4. 0.
1.sup.2,5.1.sup.7,10]-3-dodecene, and
[0114] 8-ethyl-8-N-ethyl-aminocarbonyl-tetracyclo-[4. 4. 0.
1.sup.2,5.1.sup.7,10]-3-dodecene.
[0115] The structural unit (c) is preferably contained in a range
of 0.01 to 30 mol %, more preferably 0.05 to 10 mol %, particularly
preferably 0.1 to 5 mol % based on the whole structural unit.
[0116] When the proportion of the structural unit (c) contained is
0.01 mol % or higher, an elastomer obtained from the resulting
copolymer tends to have good adhesion to and compatibility with
metals, and other elastomers and resins than polyolefin. When the
proportion of the structural unit (c) is 30 mol % or lower on the
other hand, the copolymerization of the specific functional
group-containing cycloolefin with other monomers is successfully
conducted, and the resulting copolymer tends to have rubber
elasticity as an elastomer. In addition, as the result that the
amount of a polymerization catalyst used may become less, a
high-molecular weight copolymer is easy to be provided.
[0117] The structural unit (d) is a structural unit derived from a
nonconjugated diene and contained in the copolymer as needed.
[0118] As specific examples of the nonconjugated diene used for
forming the structural unit (d), may be mentioned:
[0119] linear acyclic dienes such as 1,4-hexadiene, 1,6-octadiene
and 1,5-hexadiene,
[0120] branched-chain acyclic dienes such as
5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene,
5,7-dimethyl-1,6-octadiene, 3,7-dimethyl-1,7-octadiene,
7-methyl-1,6-octadiene and dihydromyrcene, and
[0121] alicyclic dienes such as tetrahydroindene,
methyl-tetrahydroindene, dicyclopentadiene, bicyclo[2. 2.
1]-hept-2,5-diene, 5-methylene-2-norbornene,
5-ethylidene-2-norbornene, 5-propenyl-2-norbornene,
5-isopropylidene-2-norbornene, 5-cyclohexylidene-2-norbornene and
5-vinyl-2-norbornene. Those compounds may be used either singly or
in any combination thereof.
[0122] Of the above-mentioned nonconjugated dienes, are preferred
1,4-hexadiene, 5-methylene-2-norbornene and
5-ethylidene-2-norbornene.
[0123] The structural unit (d) is preferably contained in a range
of 0 to 12 mol %, more preferably 0 to 8 mol %, particularly
preferably 0 to 5 mol % based on the whole structural unit. When
the proportion of the structural unit (d) contained is 12 mol % or
lower, an elastomer obtained from the resulting copolymer tends to
have good durability.
[0124] The functional group-containing olefin copolymers according
to the present invention have an intrinsic viscosity [.eta.]
ranging from 0.1 to 10 dl/g, preferably from 0.1 to 7 dl/g,
particularly preferably from 0.1 to 5 dl/g as measured in decalin
at 135.degree. C.
[0125] When the intrinsic viscosity [.eta.] is 0.1 dl/g or higher,
such a copolymer tends to provide an elastomer having rubber
elasticity by vulcanizing or crosslinking it. When the intrinsic
viscosity [.eta.] is 10 dl/g or lower, such a copolymer tends to
have good molding and processing ability.
[0126] The functional group-containing olefin copolymers according
to the present invention preferably have an weight average
molecular weight Mw of 1,000 to 3,000,000, more preferably 3,000 to
1,000,000, particularly preferably 5,000 to 700,000 in terms of
polystyrene as measured at 135.degree. C. by gel permeation
chromatography making use of o-dichlorobenzene as a solvent, and
have a number average molecular weight Mn of 500 to 1,000,000, more
preferably 1,000 to 500,000, particularly preferably 2,000 to
300,000 in terms of polystyrene.
[0127] In the functional group-containing olefin copolymers
according to the present invention, the glass transition
temperature is preferably -90 to 50.degree. C., more preferably -70
to 10.degree. C. Such a copolymer can provide an elastomer having
sufficient elasticity.
[0128] The glass transition temperature of the functional
group-containing olefin copolymer can be measured by means of a
differential scanning calorimeter (DSC).
[0129] According to the functional group-containing olefin
copolymers according to the present invention, the structural unit
(c) has the specific functional group (X.sup.1 and/or X.sup.2) ,
and so elastomers having high adhesion to metals, high adhesion and
compatibility with other elastomers and resins than polyolefins and
excellent coating property and printability are provided.
[0130] Since no hydrogen atom is bonded to the carbon atom to which
the specific functional group (X.sup.1 and/or X.sup.2) is bonded in
the structural unit (c), and so no tertiary hydrogen atom being apt
to separate from the bonded carbon atom to produce a radical is
present, scission of a molecular chain, oxidation and separation of
a substituent group containing the functional group due to the
formation of the radical are prevented. As a result, no or little
deterioration is caused, and excellent durability is achieved.
[0131] Further, since an aliphatic hydrocarbon group is bonded to
the carbon atom to which the specific functional group (X.sup.1
and/or X.sup.2) is bonded in the structural unit (c), the specific
functional group-containing cycloolefin used as a monomer gives off
no or little odor even when the specific functional group is a
carboxyl group. Therefore, the resulting copolymer gives off no or
little odor.
[0132] Since the functional group-containing olefin copolymers
according to the present invention have such properties as
described above, they can provide elastomers suitable for use as
materials for automotive parts, mechanical parts, construction
materials, etc.
[0133] Since the functional group-containing olefin copolymers
according to the present invention have high compatibility with
other polymers, elastomers having good co-crosslinking ability can
be provided when they are mixed with other elastomer materials, for
example, nitrile rubber, chloroprene rubber, chlorinated
polyethylene rubber, halogenated butyl rubber, acrylic rubber,
ethylene-acrylic copolymer rubber, hydrogenated nitrile rubber,
etc. to conduct crosslinking.
[0134] In addition, the functional group-containing olefin
copolymers according to the present invention can be used as
modifiers for polypropylene, polyethylene, hydrogenated
styrene/butadiene random copolymers, hydrogenated styrene/butadiene
block copolymers, hydrogenated styrene/isoprene block copolymers,
etc. Such materials are suitable for use as automotive exterior or
interior materials such as various films, bumpers, instrument
panels and door trims.
[0135] According to the functional group-containing olefin
copolymers according to the present invention, their graft
copolymers with polyester such as polybutylene terephthalate,
polyethylene terephthalate; polyamide and polyurethane can be
obtained by using the functional group in the structural unit (c)
as a starting point, whereby resins improved in impact resistance,
thermoplastic elastomer having high heat resistance, etc. can be
provided.
[0136] Such functional group-containing olefin copolymers can be
produced in the following manner.
[0137] The specific functional group-containing cycloolefin is
first reacted with an organometallic compound (hereinafter referred
to as "the specific organometallic compound") comprising a metal
selected from metals of Groups 2, 12 and 13 of the periodic table,
whereby the functional group (group X.sup.1 and/or group X.sup.2)
in the specific functional group-containing cycloolefin is
subjected to a masking treatment.
[0138] Specific examples of the specific organometallic compound
used in the masking treatment include diethylzinc,
dibutylmagnesium, ethylmagnesium chloride, butylmagnesium chloride,
trimethylaluminum, triethylaluminum, triisobutylaluminum,
trihexylaluminum, diisobutylaluminum hydride, diethylaluminum
hydride, ethylaluminum dihydride, diethylaluminum ethoxide,
ethylaluminum diethoxide, dibutylaluminum ethoxide, dibutylaluminum
butoxide, diisobutylaluminum dibutoxide, diisobutylaluminum
isopropoxide, diisobutylaluminum 2-ethylhexyloxide,
isobutylaluminum butoxide, isobutylaluminum 2-ethylhexyloxide,
diethylaluminum chloride, ethylaluminum dichloride, diethylaluminum
bromide, ethylaluminum sesquichloride, and methylalumoxane,
ethylalumoxane and butylalumoxane obtained by the reaction of water
or copper sulfate hydrate with a trialkylaluminum.
[0139] Of these,, the organoaluminum compounds are preferred.
Examples of particularly preferred organoaluminum compounds include
trimethylaluminum, triethylaluminum, triisobutylaluminum,
diisobutylaluminum hydride, diethylaluminum chloride and
ethylaluminum sesquichloride.
[0140] The masking treatment, i.e., the reaction of the specific
functional group-containing cycloolefin with the specific
organometallic compound is preferably conducted in the presence of
an inert solvent or diluent under an atmosphere of an inert gas
such as nitrogen gas, argon gas or helium gas.
[0141] As the inert solvent or diluent, may be used aliphatic
hydrocarbons such as butane, pentane, hexane, heptane and octane,
cyclic hydrocarbons such as cyclopentane, cyclohexane and
methylcyclopentane, and aromatic compounds and halogenated
hydrocarbons such as benzene, toluene, xylene, chlorobenzene,
dichloroethane and dichloromethane.
[0142] The specific organometallic compound is preferably used in a
proportion of at least 0.8 equivalents, more preferably 0.9 to 1.5
equivalents per equivalent of the functional group in the specific
functional group-containing cycloolefin. If this proportion is too
low, a great amount of the functional group remains unmasked, and
so the catalytic activity in a polymerization treatment, which will
be described subsequently, may be lowered in some cases, and the
polymerization reaction may not proceed sufficiently.
[0143] The conditions for the reaction of the specific functional
group-containing cycloolefin with the specific organometallic
compound vary according to the kinds of the specific organometallic
compound and specific functional group-containing cycloolefin used.
However, the reaction time is generally 2 minutes to 10 hours,
preferably 10 minutes to 2 hours, and the reaction temperature is
generally -10 to 60.degree. C., preferably 10 to 40.degree. C.
[0144] The specific functional group-containing cycloolefin
subjected to the masking treatment in such a manner is preferably
stored at a temperature of 30.degree. C. or lower until it is
subjected to a polymerization treatment. The occurrence of side
reactions during the storing can be prevented thereby.
[0145] When an unreacted metal-carbon bond is present in the masked
compound, a compound having a branched structure, for example, an
alcohol such as isopropanol, sec-butanol, tert-butanol or
2-ethylhexanol, or a phenol such as 2,6-di-tert-butylcresol,
2,6-di-tert-butylphenol, 2,6-dimethylcresol or 2,6-dimethylphenol,
may also be added.
[0146] In the production process according to the present
invention, the specific functional group-containing cycloolefin
subjected to the masking treatment, ethylene, the specific
.alpha.-olefin and a nonconjugated diene optionally used are
subjected to a polymerization treatment.
[0147] In the polymerization treatment of these monomers, a
catalyst composed of a transition metal compound, preferably a
compound of a metal selected from metals of Groups 4 and 5 of the
periodic table, and an organoaluminum compound is used.
[0148] As the catalyst, a catalyst capable of providing a
copolymer, in which the respective structural units are arranged at
comparatively random manner in the copolymerization of ethylene
.alpha.-olefin and non-conjugated diene is preferably used.
Specific examples of the catalyst system include the following
systems.
[0149] (1) A catalyst system composed of a hydrocarbon
compound-soluble vanadium compound and an organoaluminum compound,
in which at least one chlorine atom is contained in any one of the
vanadium compound and the organoaluminum compound, or both
compounds.
[0150] In this catalyst system, as the vanadium compound, may be
used a compound represented by the following general formula (3),
VCl.sub.4, VO(acac).sub.2, V(acac).sub.3 (in which "acac" means an
acetylacetonato group), or a compound represented by the following
general formula (4).
[0151] General formula (3):
O=VCl.sub.k(OR.sup.4).sub.3-k
[0152] wherein R.sup.4 means a hydrocarbon group such as an ethyl,
propyl, butyl or hexyl group, and k denotes an integer of 0 to
3.
[0153] General formula (4):
VCl.sub.3.multidot.mZ
[0154] wherein Z means a Lewis base forming a complex soluble in
hydrocarbon compounds, such as tetrahydrofuran,
2-methyl-tetrahydrofuran, 2-methoxymethyl-tetrahydrofuran or
dimethylpyridine, and m denotes an integer of 2 or 3.
[0155] As the organoaluminum compound, may be used a
trialkylaluminum compound represented by the following general
formula (5), an alkylaluminum hydride represented by the following
general formula (6) or (7), an alkylaluminum chloride represented
by the following general formula (8), (9) or (10), an alkoxy- or
phenoxy-substituted organoaluminum compound represented by the
following general formula (11) or (12), or methylalumoxane (MAO),
ethylalumoxane or butylalumoxane obtained by the reaction of water
with the above-described trialkylaluminum compound.
[0156] General formula (5):
AlR.sup.5.sub.3
[0157] General formula (6):
HAlR.sup.5.sub.2
[0158] General formula (7):
H.sub.2AlR.sup.5
[0159] General formula (8):
R.sup.5AlCl.sub.2
[0160] General formula (9):
R.sup.5.sub.3Al.sub.2Cl.sub.3
[0161] General formula (10):
R.sup.5.sub.2AlCl
[0162] General formula (11):
[0163] R.sup.5.sub.2Al (OR.sup.6)
[0164] General formula (12):
R.sup.5Al(OR.sup.6).sub.2
[0165] In the general formulae (5) to (12), R.sup.5 means a
hydrocarbon group such as a methyl, ethyl, propyl, butyl or hexyl
group, and R.sup.6 denotes a methyl, ethyl, butyl, phenyl,
tolylxylyl, 2,6-di-tert-butylphenyl,
4-methyl-2,6-di-tert-butylphenyl, 2,6-dimethylphenyl or
4-methyl-2,6-dimethylphenyl group.
[0166] In this catalyst system, an oxygen- or nitrogen-containing
electron donor such as an ester of an organic acid or inorganic
acid, ether, amine, ketone or alkoxysilane may be additionally
added to the vanadium compound and organoaluminum compound.
[0167] (2) A catalyst system composed of a titanium halide or
zirconium halide carried on silica or magnesium chloride, and an
organoaluminum compound.
[0168] In this catalyst system, as the titanium halide or zirconium
halide, may be used titanium tetrachloride, titanium tetrabromide,
zirconium tetrachloride or the like.
[0169] As the organoaluminum compound, may be used
trimethylaluminum, triethylaluminum, triisobutylaluminum,
methylalumoxane or the like.
[0170] In this catalyst system, dioctyl phthalate,
tetraalkoxysilane, diphenyldimethoxysilane or the like may be
additionally added to the above-described compounds.
[0171] (3) A catalyst system composed of a transition metal
compound comprising a metal selected from titanium, zirconium and
hafnium, which has one or two cyclopentadienyl or indenyl groups
each having a substituent selected from hydrogen, alkyl groups and
allyl group, and an organoaluminum compound containing at least 50
mol % of methylalumoxane.
[0172] Specific examples of the transition metal compound include
bis(cyclopentadienyl)dimethylzirconium,
bis-(cyclopentadienyl)diethylzirc- onium,
bis(cyclopentadienyl)methylzirconium monochloride,
ethylenebis(cyclopentadienyl)zirconium dichloride,
ethylenebis(cyclopentadienyl)methylzirconium monochloride,
methylenebis(cyclopentadienyl)zirconium dichloride,
ethylenebis(indenyl)zirconium dichloride,
ethylenebis(indenyl)dimethylzir- conium,
ethylenebis(indenyl)diphenylzirconium, ethylenebis(4, 5, 6,
7-tetrahydro-1-indenyl)dimethylzirconium,
ethylenebis(4-methyl-1-indenyl)- zirconium dichloride,
ethylenebis(2,3-dimethyl-1- indenyl)zirconium dichloride,
dimethylsilylbis(cyclopentadienyl)zirconium dichloride,
dimethylsilylbis(indenyl)zirconium dichloride,
dimethylsilylbis(dimethylc- yclopentadienyl)zirconium dichloride,
dimethylmethyl(fluorenyl)(cyclopenta- dienyl)zirconium dichloride,
diphenylmethyl(fluorenyl)(cyclopentadienyl)zi- rconium dichloride,
diphenylsilylbis(indenyl)zirconium dichloride,
dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dichloride,
bis(cyclopentadienyl)dimethyltitanium,
bis(cyclopentadienyl)methyltitaniu- m monochloride,
ethylenebis(indenyl)titanium dichloride, ethylenebis(4, 5, 6,
7-tetrahydro-1-indenyl)titanium dichloride,
methylenebis(cyclopentadie- nyl)titanium dichloride,
.eta..sup.1:.eta..sup.5-{([(tert-butyl-amido)dime- thylsilyl]-(2,
3, 4, 5-tetramethyl-1-cyclopentadienyl)}titanium dichioride and
bis(1, 1, 1-trifluoro-3-phenyl-2,4-butadionato) titanium
dichloride.
[0173] (4) A metallocene catalyst system composed of dichloride of
a bisalkyl-substituted or N-alkyl-substituted salicylaldoimine and
titanium, zirconium or hafnium, and methylalumoxane (MAO).
[0174] The polymerization treatment of the monomers is preferably
conducted in the presence of a proper solvent or diluent. As such a
solvent or diluent, may be used, for example, an aliphatic
hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon or halide
thereof. Specific examples thereof include butane, pentane, hexane,
heptane, 2-butene, 2-methyl-2-butene, cyclopentane,
methylcyclopentane, cyclohexane, isooctane, benzene, toluene,
xylene, chlorobenzene, dichloromethane and dichloroethane. These
solvents or diluents may preferably be used in a state that the
water content has been lowered to 20 ppm or lower by a distilling
treatment or adsorbing treatment.
[0175] The polymerization reaction is preferably conducted at a
temperature of 0 to 150.degree. C., particularly 10 to 100.degree.
C.
[0176] In the polymerization reaction, a molecular weight modifier
may be used as needed. Specific examples thereof include hydrogen,
diethylzinc and diisobutylaluminum hydride.
[0177] A reactor used for conducting the polymerization reaction
may be any of the batch type and the continuous type. As the
continuous type reactor, may be used a tube type reactor, tower
type reactor or vessel type reactor.
[0178] In the present invention, the polymerization treatment of
the monomers is conducted in the above-described manner, and the
resultant copolymer is then subjected to a demasking treatment,
whereby the intended functional group-containing olefin copolymer
is obtained.
[0179] When a compound, in which the specific functional group
(group X.sup.1 and/or group X.sup.2) is a hydroxyl or carboxyl
group, is used as the specific functional group-containing
cycloolefin, the demasking treatment is conducted by using an acid
having a comparatively high acidity, such as formic acid, oxalic
acid, fumaric acid, lactic acid, dioctylmonophosphoric acid,
trifluoroacetic acid, dodecylbenzenesulfonic acid,
nonylphenoxypolyethylene glycol monophosphate,
nonylphenoxypolyethylene glycol diphosphate, lauroxypolyethylene
glycol monophosphate or lauroxypolyethylene glycol diphosphate.
[0180] When a compound, in which the specific functional group
(group X.sup.1 and/or group X.sup.2) is an amino or amide group, is
used as the specific functional group-containing cycloolefin on the
other hand, the demasking treatment is conducted by using an
alcoholate having a strong basicity, such as an alcoholate of
tert-butanol with lithium, sodium or potassium, an alcoholate of
amyl alcohol with lithium, sodium or potassium, the lithium, sodium
or potassium salt of octanoic acid, or the lithium or potassium
salt of nonylphenol, phenol or an alkali metal salt of an organic
carboxylic acid.
[0181] In the production process according to the present
invention, a treatment for removing remaining demasking agent,
polymerization catalyst and the like is preferably conducted by
passing the thus-obtained polymer solution containing the
functional group-containing olefin copolymer through an adsorption
column in which silica, alumina, diatomaceous earth has been
packed, or adding a great amount of water, alcohol or the like to
the polymer solution to wash it.
[0182] A publicly known phenolic, phosphorus-containing or
sulfur-containing antioxidant may be added to the polymer solution
with a view toward improving the stability of the functional
group-containing olefin copolymer.
[0183] Steam is blown into the polymer solution, thereby conducting
a removal treatment of the solvent, and solids are then separated
from the resulting slurry and dehydrated and dried by means of a
screw type squeezer, extruder, heated roll or the like, thereby
obtaining the functional group-containing olefin copolymer as a
solid. Alternatively, the polymer solution is heated to concentrate
it, and the concentrate is dried by means of a vented extruder,
thereby obtaining the functional group-containing olefin copolymer
as a solid.
[0184] According to the process described above, the functional
group in the specific functional group-containing cycloolefin is
subjected to the masking treatment with the specific organometallic
compound. Therefore, masking of such a functional group is assured,
and consequently the activity of the catalyst is prevented from
being lowered in the polymerization reaction, and no obstruction to
the polymerization reaction is offered. As a result, the intended
functional group-containing olefin copolymer can be exactly
produced.
[0185] The rubber composition according to the present invention
comprises a component (A) composed of the functional
group-containing olefin copolymer as described above, and a
component (B) composed of a vulcanizing agent and/or a crosslinking
agent and further contains a component (C) composed of an olefin
copolymer having no functional group as needed.
[0186] No particular limitation is imposed on the vulcanizing agent
as the component (B) used in the rubber composition according to
the present invention, and specific examples thereof include sulfur
such as sulfur powder, precipitated sulfur, colloidal sulfur and
insoluble sulfur; inorganic vulcanizing agents such as sulfur
chloride, selenium and tellurium; and sulfur-containing organic
compounds such as morpholine disulfide, alkylphenol disulfides,
thiuram disulfides and dithiocarbamates. These vulcanizing agents
may be used either singly or in any combination thereof.
[0187] The proportion of the vulcanizing agent used is generally
0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight per
100 parts by weight of the component (A).
[0188] In the rubber composition according to the present
invention, a vulcanization accelerator may be used in combination
with the vulcanizing agent.
[0189] Specific examples of such a vulcanization accelerator
include aldehyde ammonia type vulcanization accelerators such as
hexamethylenetetramine; guanidine type vulcanization accelerators
such as diphenyl-guanidine, di-(o-tolyl)guanidine and
o-tolylbiguanidine; thiourea type vulcanization accelerators such
as thiocarboanilide, di-(o-tolyl)thiourea, N,N'-diethylthiourea,
tetramethylthiourea, trimethylthiourea and dilaurylthiourea;
thiazole type vulcanization accelerators such as
mercaptobenzothiazole, dibenzothiazyl disulfide,
2-(4-morpholinothio)benzothiazole,
2-(2,4-dinitrophenyl)-mercaptobenzothi- azole and
(N,N'-diethylthiocarbamoylthio)benzothiazole; sulfenamide type
vulcanization accelerators such as N-t-butyl-2-benzothiazyl
sulfenamide, N,N'-dicyclohexyl-2-benzothiazyl sulfenamide,
N,N'-diisopropyl-2-benzothi- azyl sulfenamide and
N-cyclohexyl-2-benzothiazyl sulfenamide; thiuram type vulcanization
accelerators such as tetramethylthiuram disulfide,
tetraethylthiuram disulfide, tetra-n-butylthiuram disulfide,
tetramethylthiuram monosulfide and dipentamethylenethiuram
tetrasulfide; carbamate type vulcanization accelerators such as
zinc dimethylthiocarbamate, zinc diethylthiocarbamate, zinc
di-n-butylthiocarbamate, zinc ethylphenylthiocarbamate, sodium
dimethyldithiocarbamate, copper dimethyldithiocarbamate, tellurium
dimethylthiocarbamate and iron dimethylthiocarbamate; and
xanthogenate type vulcanization accelerators such as zinc
butylthioxanthogenate. These vulcanization accelerators may be used
either singly or in any combination thereof.
[0190] The proportion of the vulcanization accelerator used is
generally 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by
weight per 100 parts by weight of the component (A).
[0191] To the rubber composition according to the present
invention, may be added a vulcanization acceleration aid, as
needed, in addition to the vulcanizing agent and vulcanization
accelerator.
[0192] As specific examples of such a vulcanization acceleration
aid, may be mentioned metal oxides such as magnesium oxide, zinc
white, litharge, red lead and lead white; and organic acids or
organic acid salts such as stearic acid, oleic acid and zinc
stearate. Of these, zinc white and stearic acid one preferred.
These vulcanization acceleration aids may be used either singly or
in any combination thereof.
[0193] The proportion of the vulcanization acceleration aid used is
generally 0.5 to 20 parts by weight per 100 parts by weight of the
component (A).
[0194] No particular limitation is imposed on the crosslinking
agent as the component (B) used in the rubber composition according
to the present invention, and specific examples thereof include
organic peroxides such as 1,1-di-tert-butylperoxy-3, 3,
5-trimethyl-cyclohexane, di-tert-butyl peroxide, dicumyl peroxide,
tert-butylcumyl peroxide,
2,5-dimethyl-2,5-di(tert-butylperoxy)hexane and
1,3-bis(tert-butylperoxy-- isopropyl)ben2-ene. These crosslinking
agents may be used either singly or in any combination thereof.
[0195] The proportion of the crosslinking agent used is generally
0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight per
100 parts by weight of the component (A).
[0196] In the rubber composition according to the present
invention, a crosslinking aid may also be used in combination with
the crosslinking agent.
[0197] Specific examples of such a crosslinking aid include sulfur
and sulfur compounds such as sulfur and dipentamethylenethiuram
tetrasulfide; polyfunctional monomers such as ethylene diacrylate,
ethylene dimethacrylate, polyethylene diacrylate, polyethylene
dimethacrylate, divinylbenzene, diallyl phthalate, triallyl
cyanurate, m-phenylene bismaleimide and toluylene bismaleimide; and
oxime compounds such as p-quinone oxime and p,p'-dibenzoylquinone
oxime. These crosslinking aids may be used either singly or in any
combination thereof.
[0198] The proportion of the crosslinking aid used is generally 0.5
to 20 parts by weight per 100 parts by weight of the component
(A).
[0199] In the rubber composition according to the present
invention, the component (C) is an olefin copolymer having no
functional group and contained as needed.
[0200] No particular limitation is imposed on such an olefin
copolymer having no functional group so far as it is commonly used
in rubber compositions. It is however preferable to use a copolymer
comprising a structural unit derived from ethylene and a structural
unit derived from an .alpha.-olefin having 3 to 12 carbon atoms, or
a copolymer comprising a structural unit derived from ethylene, a
structural unit derived from an .alpha.-olefin having 3 to 12
carbon atoms and a structural unit derived from a nonconjugated
diene.
[0201] As specific examples of the .alpha.-olefin having 3 to 12
carbon atoms, may be mentioned those mentioned as examples of the
specific .alpha.-olefin for forming the structural unit (b) in the
functional group-containing olefin copolymer which is the component
(A).
[0202] As specific examples of the nonconjugated diene, may be
mentioned those mentioned as examples of the nonconjugated diene
for forming the structural unit (d) in the functional
group-containing olefin copolymer which is the component (A).
[0203] The olefin copolymer having no functional group, which is
the component (C), preferably has an weight average molecular
weight Mw of 1,000 to 3,000,000, more preferably 3,000 to
2,500,000, particularly preferably 5,000 to 2,000,000 in terms of
polystyrene as measured at 135.degree. C. by gel permeation
chromatography making use of o-dichlorobenzene as a solvent, and
has a number average molecular weight Mn of 500 to 1,000,000, more
preferably 1,500 to 800,000, particularly preferably 2,500 to
600,000 in terms of polystyrene.
[0204] When the component (C) is contained in the rubber
composition according to the present invention, a ratio of the
component (A) to the component (C) is preferably 1:99 to 99:1, more
preferably 1:99 to 50:50, still more preferably 3:97 to 30:70 in
terms of a weight ratio.
[0205] In the rubber composition according to the present
invention, may be contained a filler or softening agent.
[0206] As specific examples of the filler, may be mentioned carbon
black such as SRF (semi-reinforcing furnace), FEF (fast extrusion
furnace), HAF (high abrasion furnace), ISAF (intermediate super
abrasion furnace), SAF (super abrasion furnace), FT (fine thermal)
and MT (medium thermal); and inorganic fillers such as white
carbon, finely particulate magnesium silicate, calcium carbonate,
magnesium carbonate, clay and talc. These fillers may be used
either singly or in any combination thereof.
[0207] The proportion of the filler used is generally 10 to 200
parts by weight, preferably 10 to 100 parts by weight per 100 parts
by weight of the component (A).
[0208] As specific examples of the softening agent, may be
mentioned process oils such as aromatic oil, naphthenic oil and
paraffin oil commonly used as compounding additives for rubber,
vegetable oils such as coconut oil, and synthetic oils such as
alkylbenzene oil. Of these, the process oils are preferred, with
paraffin oil being particularly preferred. These softening agents
may be used either singly or in any combination thereof.
[0209] The proportion of the softening agent used is generally 10
to 130 parts by weight, preferably 20 to 100 parts by weight per
100 parts by weight of the component (A).
[0210] Since the rubber compositions according to the present
invention contain the functional group-containing olefin copolymer
as the component (A), they permit providing elastomers which are
high in adhesion to and compatibility with other materials, coating
property and printability and excellent in durability, mechanical
properties and abrasion resistance, and give off no or little
odor.
[0211] The present invention will hereinafter be described
specifically by the following examples. However, the present
invention is not limited by these examples.
EXAMPLE 1
[0212] A 2-L separable flask purged with nitrogen was charged with
960 mL of hexane and 5 mL of a 0.5 mol/L hexane solution
(containing 2.5 mmol of 5-methyl-5-carboxy-bicyclo[2. 2.
1]-2-heptene) of 5-methyl-5-carboxy-bicy- clo[2. 2. 1]-2-heptene.
While stirring the resultant mixture, 2.5 mmol of
Al.sub.2(C.sub.2H.sub.5).sub.3Cl.sub.3 were then added to conduct a
reaction, thereby masking the carboxyl group in
5-methyl-5-carboxy-bicycl- o[2. 2. 1]-2-heptene.
[0213] While continuously feeding a gaseous mixture of ethylene
(feed rate: 5 L/min)/propylene (feed rate: 5 L/min)/hydrogen (feed
rate: 0.5 L/min) to the resultant solution, 1.85 mL (containing 1.5
mmol of Al.sub.2(C.sub.2H.sub.5).sub.3Cl.sub.3) of a hexane
solution containing Al.sub.2(C.sub.2H.sub.5).sub.3Cl.sub.3 at a
concentration of 0.81 mol/L were then added as a catalyst, and 1.5
mL (containing 0.15 mmol of VCl.sub.4) of a hexane solution
containing VCl.sub.4 at a concentration of 0.10 mol/L were added to
conduct a copolymerization reaction of ethylene, propylene and
5-methyl-5-carboxy-bicyclo[2. 2. 1]-2-heptene at 20.degree. C. for
20 minutes.
[0214] A methanol solution containing 40 mmol of oxalic acid was
added to the resultant polymer solution, and the mixture was
stirred for 10 minutes, thereby conducting a demasking
treatment.
[0215] After 1 L of water was then added to the polymer solution,
and the mixture was stirred for 10 minutes, only the polymer
solution (organic layer) was recovered. The polymer solution was
washed 3 times with 1 L of water, thereby conducting a removal
treatment of remaining oxalic acid and the like. Thereafter, steam
was blown into the polymer solution, thereby conducting a removal
treatment of the solvent, and solids were then separated from the
resultant slurry and dried by means of a heated roll, thereby
obtaining 16.5 g of a functional group-containing olefin copolymer
as a solid. No odor was observed in the functional group-containing
olefin copolymer thus obtained.
[0216] The functional group-containing olefin copolymer was
analyzed. As a result, it was found that the content of the
structural unit derived from ethylene was 56.1 mol %, the content
of the structural unit derived from propylene was 43.7 mol %, and
the content of the structural unit derived from
5-methyl-5-carboxy-bicyclo-[2. 2. 1]-2-heptene was 0.2 mol %.
[0217] The intrinsic viscosity [.eta.] was found to be 1.7 dl/g as
measured in decalin at 135.degree. C., and the weight average
molecular weight Mw be 19.6.times.10.sup.4 in terms of polystyrene
as measured by gel permeation chromatography and number average
molecular weight Mn be 7.0.times.10.sup.4 in terms of
polystyrene.
[0218] The glass transition temperature was -57.5.degree. C. as
measured by means of a differential scanning calorimeter (DSC).
[0219] The thus-obtained functional group-containing olefin
copolymer was subjected to a pressing treatment at 160.degree. C.
for 10 minutes by an electric heat press and then analyzed. As a
result, the content of the structural unit derived from
5-methyl-5-carboxy-bicyclo-[2. 2. 1]-2-heptene was found to be 0.2
mol %. This value was the same as the value before the pressing
treatment. It was hence confirmed that the copolymer has excellent
durability.
[0220] The functional group-containing olefin copolymer was
subjected to a 90-degree peeling test to a polyester film in
accordance with the testing method for peeling prescribed in JIS Z
0237. As a result, the peel strength was found to be 0.8 newton/2.5
cm.
EXAMPLE 2
[0221] A functional group-containing olefin copolymer was obtained
in an amount of 15.0 g in the same manner as in Example 1 except
that Al(iso-C.sub.4H.sub.9).sub.3 was used in place of Al.sub.2
(C.sub.2H.sub.5).sub.3Cl.sub.3 in the masking treatment of
5-methyl-5-carboxy-bicyclo[2. 2. 1]-2-heptene.
[0222] The functional group-containing olefin copolymer thus
obtained was analyzed. As a result, it was found that the content
of the structural unit derived from ethylene was 70.0 mol %, the
content of the structural unit derived from propylene was 29.7 mol
%, and the content of the structural unit derived from
5-methyl-5-carboxy-bicyclo[2. 2. 1]-2-heptene was 0.3 mol %.
[0223] The intrinsic viscosity [.eta.] was found to be 1.9 dl/g as
measured in decalin at 135.degree. C., and the weight average
molecular weight Mw be 170,000 in terms of polystyrene as measured
by gel permeation chromatography and number average molecular
weight Mn be 75,000 in terms of polystyrene.
[0224] The glass transition temperature was -52.0.degree. C. as
measured by means of a differential scanning calorimeter (DSC).
[0225] The thus-obtained functional group-containing olefin
copolymer was subjected to a pressing treatment at 160.degree. C.
for 10 minutes by an electric heat press and then analyzed. As a
result, the content of the structural unit derived from
5-methyl-5-carboxy-bicyclo-[2. 2. 1]-2-heptene was found to be 0.3
mol %. This value was the same as the value before the pressing
treatment. It was hence confirmed that the copolymer has excellent
durability.
[0226] The functional group-containing olefin copolymer was
subjected to a 90-degree peeling test to a polyester film in
accordance with the testing method for peeling prescribed in JIS Z
0237. As a result, the peel strength was found to be 1.0 newton/2.5
cm.
EXAMPLE 3
[0227] A functional group-containing olefin copolymer was obtained
in an amount of 16.7 g in the same manner as in Example 1 except
that the amounts of 5-methyl-5-carboxy-bicyclo[2. 2. 1]-2-heptene
and Al.sub.2(C.sub.2H.sub.5).sub.3Cl.sub.3 used in the masking
treatment were changed from 2.5 mmol to 10.0 mmol and from 2.5 mmol
to 10.0 mmol, respectively, and VOCl.sub.3, was used in place of
VCl.sub.4 as the polymerization catalyst.
[0228] The functional group-containing olefin copolymer thus
obtained was analyzed. As a result, it was found that the content
of the structural unit derived from ethylene was 56.8 mol %, the
content of the structural unit derived from propylene was 42.4 mol
%, and the content of the structural unit derived from
5-methyl-5-carboxy-bicyclo[2. 2. 1]-2-heptene was 0.8 mol %.
[0229] The intrinsic viscosity [.eta.] was found to be 1.2 dl/g as
measured in decalin at 135.degree. C., and the weight average
molecular weight Mw be 250,000 in terms of polystyrene as measured
by gel permeation chromatography and number average molecular
weight Mn be 100,000 in terms of polystyrene.
[0230] The glass transition temperature was -53.3.degree. C. as
measured by means of a differential scanning calorimeter (DSC).
[0231] The thus-obtained functional group-containing olefin
copolymer was subjected to a pressing treatment at 160.degree. C.
for 10 minutes by an electric heat press and then analyzed. As a
result, the content of the structural unit derived from
5-methyl-5-carboxy-bicyclo-[2. 2. 1]-2-heptene was found to be 0.8
mol %. This value was the same as the value before the pressing
treatment. It was hence confirmed that the copolymer has excellent
durability.
[0232] The functional group-containing olefin copolymer was
subjected to a 90-degree peeling test to a polyester film in
accordance with the testing method for peeling prescribed in JIS Z
0237. As a result, the peel strength was found to be 0.8 newton/2.5
cm.
Comparative Example 1
[0233] A functional group-containing olefin copolymer was obtained
in an amount of 16.5 g in the same manner as in Example 1 except
that 5-carboxy-bicyclo[2. 2. 1]-2-heptene was used in place of
5-methyl-5-carboxy-bicyclo[2. 2. 1]-2-heptene. A strong odor was
observed in the functional group-containing olefin copolymer thus
obtained.
[0234] The functional group-containing olefin copolymer was
analyzed. As a result, it was found that the content of the
structural unit derived from ethylene was 56.8 mol %, the content
of the structural unit derived from propylene was 43.0 mol %, and
the content of the structural unit derived from
5-carboxy-bicyclo[2. 2. 1]-2-heptene was 0.2 mol %.
[0235] The intrinsic viscosity [.eta.] was found to be 1.8 dl/g as
measured in decalin at 135.degree. C., and the weight average
molecular weight Mw be 20.1.times.10.sup.4 in terms of polystyrene
as measured by gel permeation chromatography and number average
molecular weight Mn be 7.2.times.10.sup.4 in terms of
polystyrene.
[0236] The glass transition temperature was -57.0.degree. C. as
measured by means of a differential scanning calorimeter (DSC).
[0237] The thus-obtained functional group-containing olefin
copolymer was subjected to a pressing treatment at 160.degree. C.
for 10 minutes by an electric heat press and then analyzed. As a
result, the content of the structural unit derived from
5-carboxy-bicyclo[2. 2. 1]-2-heptene was found to be 0.1 mol %. The
content was extremely lowered compared with the value before the
pressing treatment. It was hence confirmed that the copolymer has
poor durability.
Comparative Example 2
[0238] A functional group-containing olefin copolymer was produced
in the same manner as in Example 1 except that a methyl ester of
5-carboxy-bicyclo[2. 2. 1]-2-heptene was used in place of
5-methyl-5-carboxy-bicyclo[2. 2. 1]-2-heptene, and neither masking
treatment nor demasking treatment was conducted. As a result, the
yield was 2.0 g. It was hence confirmed that the polymerization
reaction is not allowed to sufficiently proceed.
Comparative Example 3
[0239] It was attempted to produce a functional group-containing
olefin copolymer in the same manner as in Example 1 except that a
tert-butyl ester of 5-carboxy-bicyclo[2. 2. 1]-2-heptene was used
in place of 5-methyl-5-carboxy-bicyclo[2. 2. 1]-2-heptene, and
neither masking treatment nor demasking treatment was conducted.
However, no olefin copolymer was obtained at all. It was hence
confirmed that the polymerization reaction is not allowed to
proceed.
Comparative Example 4
[0240] An olefin copolymer was produced in the same manner as in
Example 1 except that neither 5-methyl-5-carboxy-bicyclo[2. 2.
1]-2-heptene nor the masking agent was used.
[0241] The olefin copolymer thus obtained was analyzed. As a
result, it was found that the content of the structural unit
derived from ethylene was 56.8 mol %, and the content of the
structural unit derived from propylene was 43.2 mol %.
[0242] The intrinsic viscosity [.eta.] was found to be 1.75 dl/g as
measured in decalin at 135.degree. C., and the glass transition
temperature was -58.9.degree. C. as measured by means of a
differential scanning calorimeter (DSC).
[0243] The olefin copolymer was subjected to a 90-degree peeling
test to a polyester film in accordance with the testing method for
peeling prescribed in JIS Z 0237. As a result, the peel strength
was found to be 0.1 newton/2.5 cm, and so the adhesion was
extremely low compared with the olefin copolymers according to
Examples 1 to 3.
EXAMPLE 4
[0244] A 3-L separable flask purged with nitrogen was charged with
2,000 mL of hexane and 70 mL of a 0.5 mol/L hexane solution
(containing 35 mmol of 5-methyl-5-carboxy-bicyclo[2. 2.
1]-2-heptene) of 5-methyl-5-carboxy-bicyclo[2. 2. 1]-2-heptene.
While stirring the resultant mixture, 42 mmol of
Al(iso-C.sub.4H.sub.9).sub.3 were then added to conduct a reaction,
thereby masking the carboxyl group in 5-methyl-5-carboxy-bicyclo[2.
2. 1]-2-heptene.
[0245] To the resultant solution, were added 2 ml of
5-ethylidene-2-norbornene. While continuously feeding a gaseous
mixture of ethylene (feed rate: 5 L/min)/propylene (feed rate: 5
L/min)/hydrogen (feed rate: 0.5 L/min) to the solution, 104 mL
(containing 84 mmol of Al.sub.2(C.sub.2H.sub.5).sub.3Cl.sub.3) of a
0.81 mol/L hexane solution of
Al.sub.2(C.sub.2H.sub.5).sub.3Cl.sub.3 were then added as a
catalyst, and 24 mL (containing 2.4 mmol of VCl.sub.4) of a 0.10
mol/L hexane solution of VCl.sub.4 were added to conduct a
copolymerization reaction of ethylene, propylene,
5-methyl-5-carboxy-bicyclo[2. 2. 1]-2-heptene and
5-ethylidene-2-norbornene at 25.degree. C. for 10 minutes.
[0246] A butanol solution containing 630 mmol of lactic acid was
added to the resultant copolymer solution, and the mixture was
stirred for 10 minutes, thereby conducting a demasking
treatment.
[0247] After 1 L of water was then added to the copolymer solution,
and the mixture was stirred for 10 minutes, only the copolymer
solution (organic layer) was recovered. The copolymer solution was
washed 3 times with 1 L of water, thereby conducting a removal
treatment of remaining lactic acid and the like. Thereafter, steam
was blown into the copolymer solution, thereby conducting a removal
treatment of the solvent, and solids were then separated from the
resultant slurry and dried by means of a heated roll, thereby
obtaining 30 g of a functional group-containing olefin copolymer as
a solid. This functional group-containing olefin copolymer is
referred to as "Copolymer (A1)". No odor was observed in Copolymer
(A1).
[0248] Copolymer (A1) was analyzed. As a result, it was found that
the content of the structural unit derived from ethylene was 64.7
mol %, the content of the structural unit derived from propylene
was 33 mol %, the content of the structural unit derived from
5-methyl-5-carboxy-bicyclo[2. 2. 1]-2-heptene was 1.0 mol %, and
the content of the structural unit derived from
5-ethylidene-2-norbornene was 1.3 mol %.
[0249] The intrinsic viscosity [.eta.] of Copolymer (Al) was found
to be 1.77 dl/g as measured in decalin at 135.degree. C., and the
weight average molecular weight Mw be 18.7.times.10.sup.4 in terms
of polystyrene as measured by gel permeation chromatography and
number average molecular weight Mn be 8.2.times.10.sup.4 in terms
of polystyrene.
[0250] The glass transition temperature was -47.4.degree. C. as
measured by means of a differential scanning calorimeter (DSC).
[0251] In a Laboplast mill having an internal volume of 250 mL, 100
parts by weight of Copolymer (A1), 50 parts by weight of carbon
black (Seatos SO, trade name; product of Tokai Carbon Co., Ltd.), 1
part by weight of stearic acid and 10 parts by weight of process
oil (Fukol 2050N, trade name; product of Fujikosan Co., Ltd.) were
kneaded for 180 seconds under conditions of 60 rpm and 50.degree.
C.
[0252] To the kneaded product thus obtained, were added 5 parts by
weight of zinc oxide, 1 part by weight of tetramethylthiuram
disulfide and 5 parts by weight of mercaptobenzothiazole as a
vulcanization accelerator, and 0.5 parts by weight of sulfur, and
the resultant mixture was kneaded for 5 minutes by a 10-inch roll
kept at 50.degree. C., thereby obtaining a rubber composition.
EXAMPLES 5 to 7
[0253] Functional group-containing olefin copolymers containing the
respective structural units in their corresponding proportions
shown in Table 1 were produced in the same manner as in Example 4
except that the amounts of 5-methyl-5-carboxy-bicyclo[2. 2.
1]-2-heptene and 5-ethylidene-2-norbornene used were changed, and
the feed rates of ethylene and propylene were changed. The
functional group-containing olefin copolymers thus obtained are
referred to as "Copolymer (A2)", "Copolymer (A3)" and "Copolymer
(A4)", respectively.
[0254] With respect to Copolymers (A2) to (A4) thus obtained, the
intrinsic viscosities [.eta.] as measured in decalin at 135.degree.
C., the weight average molecular weights Mw in terms of polystyrene
as measured by gel permeation chromatography and number average
molecular weights Mn in terms of polystyrene, and the glass
transition temperatures as measured by means of a differential
scanning calorimeter (DSC) are shown in Table 1.
[0255] Rubber compositions were obtained in the same manner as in
Example 4 except that Copolymers (A2), (A3) and (A4) were
separately used in place of Copolymer (A1).
EXAMPLE 8
[0256] A functional group-containing olefin copolymer containing
the respective structural units in its corresponding proportions
shown in Table 1 was produced in the same manner as in Example 4
except that no 5-ethylidene-2-norbornene was used, the amount of
5-methyl-5-carboxy-bicy- clo[2. 2. 1]-2-heptene used was changed,
and the feed rates of ethylene and propylene were changed. The
functional group-containing olefin copolymer thus obtained is
referred to as "Copolymer (A5)".
[0257] With respect to Copolymers (A5) thus obtained, the intrinsic
viscosity [.eta.] as measured in decalin at 135.degree. C., the
weight average molecular weight Mw in terms of polystyrene as
measured by gel permeation chromatography and number average
molecular weight Mn in terms of polystyrene, and the glass
transition temperature as measured by means of a differential
scanning calorimeter (DSC) are shown in Table 1.
[0258] A rubber composition was obtained in the same manner as in
Example 4 except that 10 parts by weight of Copolymers (A5) and 90
parts by weight of an ethylene/propylene/5-ethylidene-2-norbornene
copolymer (hereinafter referred to as "Copolymer (C1)") were used
in place of 100 parts by weight of Copolymer (A1).
[0259] The above-described Copolymer (C1) is such that the
structural unit derived from ethylene is 65.3 mol %, the structural
unit derived from propylene is 33.6 mol %, the structural unit
derived from 5-ethylidene-2-norbornene is 1.1 mol %, the intrinsic
viscosity [.eta.] is 1.75 dl/g as measured in decalin at
135.degree. C., and the weight average molecular weights Mw is
17.3.times.10.sup.4 in terms of polystyrene as measured by gel
permeation chromatography and number average molecular weights Mn
is 7.5.times.10.sup.4 in terms of polystyrene.
[0260] A copolymer mixture was prepared by kneading 10 parts by
weight of Copolymer (AS) and 90 parts by weight of Copolymer (C1),
and the intrinsic viscosity [.eta.] thereof was measured in decalin
at 135.degree. C. and found to be 1.58 dl/g. The contents of the
respective structural units in this copolymer mixture were as
follows:
[0261] The structural unit derived from ethylene being 64.9 mol %,
the structural unit derived from propylene being 34 mol %, the
structural unit derived from 5-methyl-5-carboxy-bicyclo[2. 2.
1]-2-heptene being 0.1 mol %, and the structural unit derived from
5-ethylidene-2-norbornene being 1.0 mol %.
Comparative Examples 5 to 7
[0262] Olefin copolymers having no functional group and containing
the respective structural units in their corresponding proportions
shown in Table 1 were produced in the same manner as in Example 4
except that no 5-methyl-5-carboxy-bicyclo[2. 2. 1]-2-heptene was
used, the amount of 5-ethylidene-2-norbornene used was changed, and
the feed rates of ethylene and propylene were changed. The olefin
copolymers thus obtained are referred to as "Copolymer (X1)",
"Copolymer (X2)" and "Copolymer (X3)", respectively.
[0263] With respect to Copolymers (X1) to (X3) thus obtained, the
intrinsic viscosities [.eta.] as measured in decalin at 135.degree.
C., the weight average molecular weights Mw in terms of polystyrene
as measured by gel permeation chromatography and number average
molecular weights Mn in terms of polystyrene, and the glass
transition temperatures as measured by means of a differential
scanning calorimeter (DSC) are shown in Table 1.
[0264] Rubber compositions were obtained in the same manner as in
Example 4 except that Copolymers (X1), (X2) and (X3) were
separately used in place of Copolymer (A1).
1 TABLE 1 Compartive Compartive Compartive Example 4 Example 5
Example 6 Example 7 Example 8 Example 5 Example 6 Example 7
Copolymer Copolymer Copolymer Copolymer Copolymer Copolymer
Copolymer Copolymer (A1) (A2) (A3) (A4) (A5) (X1) (X2) (X3)
proportion structural unit derived 64.7 75.9 75.3 69.1 61.9 64.8
75.8 66.4 of a from ethylene structural structural unit derived 33
19.4 20 29 37.1 34 23 31 (mol %) from propylene structural unit
derived 1.0 3.9 3.9 0.7 1.0 -- -- -- from MCBH *1 structural unit
derived 1.3 0.8 0.8 1.2 -- 1.2 1.2 2.6 from ENB *2 intrinsic
viscosities [.eta.] 1.77 2.16 1.69 2.63 0.20 1.73 2.22 2.07 weight
average molecular 18.7 25.3 17.1 42.0 5.0 18.3 27.8 21.7 weight Mw
(.times. 10.sup.4) number average molecular 8.2 11.0 7.4 18.3 1.3
8.0 12.1 9.4 weight Mn (.times. 10.sup.4) glass transition
temperature (.degree. C.) -47.4 -44.7 -38.7 -46.2 -51.3 -50.0 -54.3
-48.7 *1 MCBH: 5-methyl-5-carboxy-bicyclo[2.2.1]-2-heptene *2 ENB:
5-ethylidene-2-norbornene
[0265] [Evaluation of rubber composition]
[0266] The respective rubber compositions obtained in Examples 4 to
8 and Comparative Examples 5 to 7 were subjected to roll retention
test, adhesion test, tensile test, hardness test and DIN abrasion
resistance test in accordance with the following respective
methods. With respect to the tensile test, hardness test and DIN
abrasion resistance test, each of the rubber compositions was
heated for 30 minutes under a pressing pressure of 150 kgf/cm.sup.2
by a hot press heated to 160.degree. C. to produce a vulcanized
rubber sheet, and specimens were prepared from this vulcanized
rubber sheet.
[0267] (1) Roll retention test:
[0268] Each of the rubber compositions obtained in Examples 4 to 8
and Comparative Examples 5 to 7 was masticated by roll mills with
roll nips adjusted to 1 mm, 2 mm and 3 mm to evaluate the rubber
composition as to roll retention in accordance with the following
5-rank standard:
[0269] 5. A rubber band is in completely close contact with the
surface of one roll, and a bank smoothly rotates;
[0270] 4. A rubber band sometimes separates from the surface of one
roll between a bank and the top of said one roll;
[0271] 3. A rubber band frequently separates from the surface of
one roll between a bank and the top of said one roll;
[0272] 2. A rubber band is not in sufficiently close contact with
the surface of one roll and sags, and mastication cannot be
conducted unless hands are lent the rubber band;
[0273] 1. A rubber band is in no close contact with the surface of
one roll and sags, and mastication cannot be conducted unless hands
are lent the rubber band.
[0274] (2) Adhesion:
[0275] Each of the rubber compositions obtained in Examples 4 to 8
and Comparative Examples 5 to 7 was subjected to an adhesion test
to a metal plate in accordance with JIS K 6256 to investigate a
peeled or broken state. The metal plate (cast iron) used in this
test was prepared by coating the surface thereof with a primer
(Metalock P, trade name, product of Toyo Kagaku Kenkyusho), drying
the primer for at least 30 minutes, further applying an adhesive
(Metalock FC, trade name; product of Toyo Kagaku Kenkyusho) to the
surface thereof and drying the adhesive for at least 30
minutes.
[0276] (3) Tensile test:
[0277] The tensile strength TB (MPa) and elongation EB (%) at break
of each sample in accordance with JIS K 6301.
[0278] (4) Hardness test:
[0279] The durometer hardness of each sample was measured in
accordance with JIS K 6253.
[0280] (5) DIN abrasion resistance test:
[0281] The abrasion resistance index of each sample was measured in
accordance with JIS K 6264.
[0282] The results are shown in Table 2.
2 TABLE 2 Comparative Comparative Comparative Example 4 Example 5
Example 6 Example 7 Example 8 Example 5 Example 6 Example 7 roll
roll mills with 5 4 5 4 5 4 3 3 retention roll nips 1 mm roll mills
with 4 3 5 3 5 2 1 1 roll nips 2 mm roll mills with 4 3 5 3 5 2 1 1
roll nips 3 mm adhesion (a peeled or broken broken broken broken
broken peeled peeled peeled broken state) material material
material material material surface surface surface the tensile
strength T.sub.B 15.5 21.3 23.1 21.7 19.5 12.2 18.8 14.1 [MPa]
elongation at break E.sub.B 330 250 220 270 360 330 320 240 [%] the
durometer hardness A 88 83 88 81 75 77 79 79 the abrasion
resistance 54 57 50 54 65 69 65 66 index
[0283] As apparent from Table 2, the rubber compositions according
to Examples 4 to 8 can provide elastomers excellent in
processability such as roll retention, and also in adhesion to
metals, mechanical strength and abrasion resistance.
[0284] On the other hand, elastomers from the rubber compositions
according to Comparative Examples 5 to 7 were inferior in
processability and adhesion to metals.
[0285] As described above, the olefin copolymers according to the
present invention permit providing elastomers which are high in
adhesion to and compatibility with other materials, coating
property and printability and excellent in durability, and give off
no or little odor.
[0286] The production process according to the present invention
permits exactly producing an olefin copolymer which can provide an
elastomer which is high in adhesion to and compatibility with other
materials, coating property and printability and excellent in
durability, and gives off no or little odor.
[0287] The rubber compositions according to the present invention
permit providing elastomers which are high in adhesion to and
compatibility with other materials, coating property and
printability and excellent in durability, mechanical properties and
abrasion resistance, and give off no or little odor. In addition,
molded or formed rubber products can be produced at low cost.
[0288] The elastomers obtained according to the present invention
are suitable for use as a material for automotive parts such as
weatherstrips and sponges, mechanical parts, electronic parts,
civil engineering and construction materials, etc.
* * * * *