Note: Descriptions are shown in the official language in which they were submitted.
CA 02328828 2001-O1-08
72932-176D
1
CYCLOOLEFIN POLYMER COMPOSITION
This is a divisional application of Canadian Patent
Application No. 2,114,480 filed January 28, 1994.
FIELD OF THE INVENTION
The present invention relates to cycloolefin polymer
compositions, and more particularly to cycloolefin polymer
compositions which are excellent in impact resistance,
transparency and heat resistance and have a good balance of
these properties.
The subject matter claimed in this divisional
application is directed to the first cycloolefin polymer
composition described on pages 5-9 and thereafter in this
specification while the subject matter claimed in the parent
application was restricted to the second cycloolefin copolymer
composition described on pages 9-10 and thereafter. It should
be noted, however, that the expression "the present invention"
or the like encompasses the subject matter claimed in both the
parent and divisional applications.
BACKGROUND OF THE INVENTION
The present applicant has found that cycloolefin
random copolymers obtained by copolymerizing ethylene and
cycloolefins such as tetracyclododecene are synthetic resins
which are excellent in transparency and well-balanced among
various properties such as heat resistance, thermal ageing
resistance, chemical resistance, solvent resistance, dielectric
properties and rigidity, and also found that these copolymers
exert excellent performance in a field of optical materials,
e.g. optical memory discs and optical fibers. Based on these
findings, the applicant has disclosed the cycloolefin random
CA 02328828 2001-O1-08
72932-176D
la
copolymers in Japanese Patent Laid-Open Publications No.
168708/1985, No. 98780/1986, No. 115912/1986, No. 115916/1986,
No. 120816/1986 and No. 252407/1987. Further, it is also known
that the copolymers described in these publications exert
excellent performance in a field of structural materials.
CA 02328828 2001-O1-08
2
However, there is yet room for improvement of the
impact resistance in the cycloolefin copolymers, though
they are excellent especially in the heat resistance and
the rigidity. Moreover, even if the impact resistance is
S improved, the transparency inherent in the cycloolefin
copolymers should be maintained.
The present applicant has also found that a
composition comprising a cycloolefin random copolymer
having a specific softening temperature (TMA) and a
specific a-olefin elastomeric copolymer can be improved in
the impact resistance without deteriorating other excellent
properties such as heat resistance, thermal aging
resistance and chemical resistance, and the present
applicant has disclosed this composition in Japanese Patent
Laid-Open Publication No. 163291/1989.
Further, the present applicant has also proposed in
Japanese Patent Laid-Open Publication No. 167318/1990 a
cycloolefin polymer composition improved in the impact
resistance which comprises a reaction product obtained by
2 0 reacting a specific cycloolefin random copolymer with a
specific soft copolymer in the presence of an organic
peroxide
However, the cycloolefin polymer compositions proposed
in Japanese Patent Laid-Open Publications No. 163241/1989
and No. 167318/1990 are not always satisfactory in the
transparency and has yet room for improvement, though they
are improved in the impact resistance.
CA 02328828 2001-O1-08
The present applicant has further proposed resin
compositions comprising cycloolefin random copolymers obtained
by copolymerizing ethylene and cycloolefins (e. g.,
tetracyclododecene) and soft polymers (rubbers) in Japanese
Patent Publication No. JP 3-255145(A).
These resin compositions are higher in the impact
resistance than the cycloolefin random copolymers as they are,
but they are desired to be much more improved in the impact
strength. Further, the resin compositions are sometimes
deteriorated in the transparency.
Moreover, in Canadian Patent Application No.
2,114,236, the present applicant has proposed a cycloolefin
copolymer obtained by copolymerizing an a-olefin and a
cycloolefin in the presence of a hydrocarbon elastomer having
a polymerizable double bond.
This cycloolefin copolymer is also good in the
impact resistance, but it is also desired to be more improved
in the transparency.
Accordingly, the present inventors have further
studied to solve such problems associated with the prior art
techniques as described abcve. As a result, they have found
that a cycloolefin polymer composition comprising two kinds of
cycloolefin polymers having specific glass transition
temperatures, specif is refract ive indexes and a specif is
difference in the- refractive index therebetween, and a
cycloolefin polymer composition obtained by radical reaction
of the above composition in the presence of an
- 3 -
72932-176
CA 02328828 2001-O1-08
. 4 '
organic peroxide and, if necessary, a radical polymerizable
polyfunctional monomer are well-balanced among the impact
resistance, the transparency and the heat resistance: and
accomplished the present invention.
S The present inventors have also found that a
cycloolefin copolymer composition, which comprises a
specific cycloolefin elastomer component [Aa] having a
polymerizable double bond and a cycloolefin copolymer
component [Ba] obtained by copolymerizing an oC-olefin of
IO two or more carbon atoms such as ethylene and a cycloolefin
in the presence of the elastomer component [Aa] and which
contains the component [Aa) in a specific amount wherein a
difference between the refractive index np(Aa) of the
component (Aa] and the refractive index no(Ba) of the
IS component [Ba] is in a specific range, is excellent
particularly in the transparency and the impact resistance;
and accomplished the present invention.
The present inventors have further found that a
cycloolefin copolymer composition, which comprises a
2 0 specific cycloolefin elastomer component [ACC) having
substantially no polymerizable double bond and a
cycloolefin elastomer [Ba] obtained by copolymerizing an
Cc-olefin of two or more carbon atoms such as ethylene and a
cycloolefi.n in the presence of the elastomer component (AOC]
2 5 and which contains the component [ACC) in a specific amount
wherein a difference between the refractive index np(AOC) of
the component [Aa] and the refractive index np(BCC) of the
CA 02328828 2001-O1-08
' S
component [BOC] is in a specific range, is also excellent
particularly in the transparency and the impact resistance;
and accomplished the present invention.
OBJECT OF THE TN«NTTn~T
The present invention is intended to solve problems
associated with the prior art techniques as described
above, and it is an object of the invention to provide a
cycloolefin polymer composition which is excellent in the
IO impact resistance, the transparency and the heat resistance
and has a good balance of these properties.
It is another object of the invention to provide a
cycloolefin copolymer composition which is improved
especially in the impact resistance and the transparency
1$ without deteriorating the excellent properties inherent in
a cycloolefin random copolymer.
SUMMARY OF TH. TNVENTTnN
The first cycloolefin polymer composition according to
2 0 the present invention comprises:
[A] a cycloolefin polymer selected from the group
consisting of:
[A-1] a cycloolefin random copolymer obtained by
copolymerizing (i) an oc-olefin of two or more carbon atoms
2 S and (ii) at least vne cycloolefin represented by the
following formula (I) or (II) and, if necessary, (iii) a
diene,
CA 02328828 2001-O1-08
6
[A-2] a ring-opening polymer of at least one
cycloolef in represented by the following formula (I) or
(II), and
[A-3] a hydrogenation product of a ring-opening
polymer of at least one cycloolefin represented by the
following formula (I) or (II),
the cycloolefin polymer [A] having an intrinsic
viscosity ('~], as measured in decalin at 135 °C, of 0.5 to
5.0 dl/g, a glass transition temperature (Tg), as measured
by DSC, of lower than 15 °C, a content of constituent units
derived from the cycloolefin of not less than 3 ~ by mol,
and a refractive index np(A), as measured at 25 °C, of
1.500 to 1.650; and
[B] a cycloolefin polymer selected from the group
consisting of:
[B-1] a cycloolefin random copolymer obtained by
copolymerizing (i) an a,-olefin of two or more carbon atoms
and (ii) at least one cycloolefin represented by the
following formula (I) or (II) and, if necessary, (iii) a
2 0 diene,
[B-2} a ring-opening polymer of at least one
cycloolefin represented by the following formula (I) or
(II), and
[B-3] a hydrogenation product of a ring-opening
2 5 polymer of at least one cycloolefin represented by the
following formula (I) or (II),
CA 02328828 2001-O1-08
7
the cycloolefin polymer [B] having an intrinsic
viscosity ['~], as measured in decalin at 135 °C, of 0.1 to
5.0 dl/g, a glass transition temperature (Tg), as measured
by DSC, of not lower than 70 °C, and a refractive index
np(B), as measured at 25 °C, of 1.500 to 1.650;
wherein a difference Onp = Ino(A) - np(B)) between the
refractive index np(A) of the cycloolefin polymer [A] and
the refractive index np(B) of the cycloolefin polymer (B]
is not more than 0.015, and a weight ratio [A]/[B] is in
the range of 8/92 to 90/60:
Ris
Ris
Rm
Rig
(I)
wherein n is 0 or 1; m is 0 or a positive integer; q is 0
1 5 or 1;
each of R1 - R18, Ra and Rb is independently a hydrogen
atom, a halogen atom, or an aliphatic, an alicyclic or an
aromatic hydrocarbon group;
CA 02328828 2001-O1-08
gis _ gia may be linked with one another to form a
monocyclic or polycyclic group which may have a double
bond; and
R15 and Rls, or Rl' and Rla may together form an
alkylidene group; or
gla gis
g1s ~ gm
l I
n
(~H2~ q ~ ~ R15
gi3 ~ ~ gla
I
m
gil gi2
p
(II)
wherein each of p and q is independently 0 or an integer of
1 or more; each of m and n is independently 0, 1 or 2;
each of R1 - R19 is independently a hydrogen atom, a
halogen atom, or an aliphatic, an alicyclic or an aromatic
hydrocarbon group, or an alkoxy group; the carbon atom to
Which R9 and R1° are linked may be bonded directly or by way
of an alkylene group of 1 - 3 carbon atoms to the carbon
atom to which R13 is linked or the carbon atom to which Rli
is linked;~~ and
R15 and Rlz, or R15 and R19 may be linked together to
form a monocyclic or polycyclic aromatic ring when each of
2 0 n and m is 0.
CA 02328828 2001-O1-08
9
The first cycloolefin polymer composition of the
invention can be modified by radical reaction thereof in
the presence of an organic peroxide and if necessary, a
radical polymerizable polyfunctional monomer.
The first cycloolefin polymer composition of the
invention and the radical reaction modified product thereof
show excellent impact resistance, transparency and heat
resistance.
In the first cycloolefin polymer composition of the
invention, the cycloolefin polymer [A] and the cycloolefin
polymer [B] are preferably cycloolefin random copolymers
[A-1] and [B-1], respectively, each obtained by
copolymerizing (i) an oc-olefin of two or more carbon atoms,
and (ii) at least one cycloolefin represented by the above
formula (I) or (II) and if necessary, (iii) a diene.
Further, the cycloolefin polymer [A] is particularly
preferably a random copolymer of an oc-olefin having two or
more carbon atoms and a cycloolefin represented by the
above formula (II) .
2 0 The cycloolefin polymer [B] is particularly preferably
a random copolymer of an oc-olefin having two or more carbon
atoms and a cycloolefin represented by the above formula
(I) .
The second cycloolefin copolymer composition according
to the present invention comprises:
[Aa] a cycloolefin elastomer component which is
obtained by copolymerizing (i) an oc-olefin of two or more
CA 02328828 2001-O1-08
carbon atoms with (11) at least one cycloolefin represented by
the above formula (I) or (II) and (iiia) a non-conjugated
diene of 5 to 20 carbon atoms, and which has a content of the
cycloolefin units of not less than 3~ by mol, an intrinsic
viscosity ['~], as measured in decalin at 135oC, of 0.5 to 5.0
dl/g, a glass transition temperature (Tg) of lower than l5oC,
a polymerizble carbon-carbon double bond and an iodine value
of 2 to 30 (g-iodine/100 g-polymer) and a refractive index
np(Aa), as measured at 25oC, of 1.500 to 1.650; and
[Ba] a cycloolefin copolymer component which is obtained
by copolymerizing (i) an a-olefin of two or more carbon atoms
and (ii) at least one cycloolefin represented by the above
formula (I) or (II) in the presence of the elastomer component
[Aa] so that the elastomer component [Aa] is at least
partially chemically bonded to the copolymer component [Ba],
wherein the component [Aa] exists in an amount of 8 to
405 by weight, and the difference!, nD = /nD(Aa) - np(Ha)~
between the refractive index np(Aa) of the component [Aa] and
the refractive index nD(Ha) of the component [Ba] is not more
than O.OI5.
In this second cycloolefin copolymer composition,
the cycloolefin elastomer component [Aa] is preferably a
copolymer of a cycloolefin represented by the formula (II),
and the cycloolefin copolymer component [Ba] is preferably a
copolymer of a cyeloolefin represented by the formula (I).
The second cycloolefin copolymer composition of the
invention has excellent properties inherent in a cycloolefin
random copolymer, and is improved particularly in the impact
- 10 -
72932-176
CA 02328828 2001-O1-08
resistance without trading off its transparency.
The third cycloolefin copolymer composition
according to the present invention comprises:
[Aa] a cycloolefin elastomer component which is
obtained by copolymerizing (i) an a-olefin of two or more
carbon atoms and (11) at least one cycloolefin represented by
the above formula (I) or (II), and which has a content of the
cycloolefin units of not less than 3~ by mol, an intrinsic
viscosity [~], as measured in decalin at 135°C, of 0.5 to 5.0
dl/g, a glass transition temperature (Tgl of lower than l5oC
and a refractive index nD(Aa), as measured at 25°C, of 1.500
to 1.650, and substantially contains no polymerizable carbon-
carbon double bond; and
[Ha] a cycloolefin copolymer component which is obtained
by copolymerizing (i) an a-olefin of two or more carbon atoms
and (11) at least one cycloolefin represented by the above
formula (I) or (II) in the presence of the elastomer component
[Aa] so that the elastomer component [Aa] is finely dispersed
in the copolymer component [Ha],
wherein the component [Aa] exists in the composition in
an amount of 8 to 40~ by weight, and a difference ~ nD =
~nD(Aa) - nD(Ha)~ between the refractive index nD(Aa) of the
component [Aa] and the refractive index nD(Ha) of the
component [Ba] is not more than 0.015.
In this invention, the cycloolefin elastomer
component [Aa] is preferably a copolymer of a cycloolefin
represented by the formula (II), and the cycloolefin copolymer
component [Ba] is preferably a copolymer of a cycloolefin
- 11 -
72932-176
CA 02328828 2001-O1-08
represented by the formula (I).
The third cycloolefin copolymer composition of the
invention has also excellent properties inherent in a
cycloolefin random copolymer, and is improved particularly in
the impact resistance without trading off its transparency.
It should be noted that although three cycloolefin
copolymer compositions are disclosed above, only the second
and third disclosed compositions are claimed.
DETAILED DESCRIPTION OF THE INVENTION
The cycloolefin polymer compositions according to
the present invention will be further described hereinafter.
The meaning of the term "polymer" used herein is not
limited to "homopolymer" but may comprehend "copolymer".
Also, the meaning of the term "polymerization" used herein is
not limited to "homopolymerization" but may comprehend
"copolymerization".
First CYCloolefin Polymer Composition
The first cycloolefin polymer composition according
to the invention is formed from:
[A] a cycloolefin polymer selected from the group
consist ing of
[A-1] a cycloolefin random copolymer obtained by
copolymerizing (i) an a-olefin of two or more carbon atoms and
(11) at least one cycloolefin represented by the formula (I)
or (II) and ~if necessary, (111) a diene,
- 12 -
72932-I76
CA 02328828 2001-O1-08
13
[A-2] a ring-opening polymer of at least one
cycloolefin represented by the formula (I) or (II), and
[A-3] a hydrogenation product of a ring-opening
polymer of at least one cycloolefin represented by the
following formula (I) or (II); and
[Bj a cycloolefin polymer selected from the group
consisting of:
[B-1] a cycloolefin random copolymer obtained by
copolymerizing (i) an oc-olefin of two or more carbon atoms
and (ii) at least one cycloolefin represented by the
formula (I) or (II) and if necessary, (iii) a diene,
[B-2] a ring-opening polymer of at least one
cycloolefin represented by the following formula (I) or
( I I ) , and
[B-3] a hydrogenation product of a ring-opening
polymer of at least one cycloolefin represented by the
formula (I) or (II) .
The cycloolefin random copolymer (A-1] and the
cycloolefin random copolymer [B-1] used in the invention
2 0 are each a cycloolefin random copolymer obtained by
copolymerizing (i) an oc-olefin of two or more carbon atoms
and at least one cycloolefin represented by the formula (I)
or (II) and, if necessary, (iii) a diene.
The a.-olefin of two or more carbon atoms (i) used for
preparing the cycloolefin random copolymer [A-1] and the
cycloolefin random copolymer [B-1] may be straight chain
or branched chain, and preferably has 2 to 20 carbon atoms.
CA 02328828 2001-O1-08
14
Examples of such oc-olefin include ethylene, propylene, 1-
butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-
pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-
hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-
ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-
dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-
eicosene. Of these, preferred is ethylene or propylene,
and particularly preferred is ethylene. These oc-olefins
may be used singly or in combination of two or more kinds.
The cycloolefin (ii) used for preparing the
cycloolefin random copolymer [A-1] and the cycloolefin
random copolymer [B-1] is a cycloolefin represented by the
formula ( I ) or ( I I ) .
The cycloolefin represented by the formula (I) or (II)
is described below in detail.
Ris
Rib
Rte
Rts
tI)
" ._1
CA 02328828 2001-O1-08
72932-176
In the formula (I), n is 0 or 1, m is 0 or a positive
integer, and q is 0 or 1. When q is 1, a ring represented
by using q is a 6-membered ring, and when q is 0, this ring
is a 5-membered ring.
5 Further, in the above formula (I) , R1 - R18, Ra and Rb
are each independently a hydrogen atom, a halogen atom, or
an aliphatic, an alicyclic or an aromatic hydrocarbon
group.
Examples of the halogen atom include fluorine atom,
IO chlorine atom, bromine atom and iodine atom.
Examples of the hydrocarbon group generally include
alkyl group of 1 - 20 carbon atoms, cycloalkyl group of 3 -
15 carbon atoms and aromatic hydrocarbon group.
Specific examples of the alkyl group include methyl
15 group, ethyl group, propyl group, isopropyl group, amyl
group, hexyl group, octyl group, decyl group, dodecyl group
and octadecyl group. These alkyl groups may be substituted
with halogen atoms.
A specific example of the cycloalkyl group is
2 0 cyclohexyl group.
Specific examples of the aromatic hydrocarbon group
include phenyl group and naphthyl group.
Moreover, in the above formula ( I ) , Rls and R16, R~~
and Rla, Rls and R1~, R16 and R18, Ris and R18, or R16 and R1'
may be linked together to form a monocyclic or polycyclic
group, and thus formed monocyclic or polycyclic group may
have a double bond. Preferably, m is 0, 1 or 2.
CA 02328828 2001-O1-08
16
Examples of the monocyclic or polycyclic group are
given below.
1 1 1 1 1
2 2 ~ 2 2 2
1
1
2 Z
S In these cyclic groups, carbon atoms attached with
numerals 1 and 2 are those to Which substituent R15 (R16) or
R18 (R19) is linked.
In the above formula (I) , R15 and R16, or R1~ and R18
may together form an alkylidene group. This alkylidene
group generally has 2 - 20 carbon atoms, and examples of
such alkylidene group include ethylidene group, propylidene
group and isopropylidene group.
Rls R19
R16 ~ R17
l I
n
(CFi2) q ~ ~ Ris
io
Ri3 ~ ~Ria
I
m
Rll R12
P
1 5 (II)
CA 02328828 2001-O1-08
1 7
In the formula (II), each of p and q is independently
0 or an integer of 1 or more, and each of m and n is
independently 0, 1 or 2.
S Further, R1 - Rl9 are each independently a hydrogen
atom, a halogen atom, or an aliphatic, an alicyclic or an
aromatic hydrocarbon group, or an alkoxy group.
In the formula (II), the halogen atom has the same
meanings as in the formula (I).
The hydrocarbon groups include generally alkyl group
of 1 - 20 carbon atoms and cycloalkyl group of 3 - 15
carbon atoms or aromatic hydrocarbon group. Specific
examples of the alkyl group include methyl group, ethyl
group, propyl group, isopropyl group, amyl group, hexyl
group, octyl group, decyl group, dodecyl group and
octadecyl group. These alkyl groups may be substituted
with halogen atoms.
The cycloalkyl groups include, for example, cyclohexyl
group.
2 0 The aromatic hydrocarbon groups include, for example,
aryl group and aralkyl group. Specific examples include
phenyl group, tolyl group, naphthyl group, benzyl group and
phenylethyl group.
Specific examples of the alkoxy group include methoxy
2 5 group, ethoxy group and propoxy group.
The carbon atom to which R9 and Rlo are linked may be
bonded directly or by way of an alkylene group of 1 - 3
CA 02328828 2001-O1-08
18
carbon atoms to the carbon atom to which R13 is linked or
the carbon atom to which R11 is linked. In the latter
case, R9 and R13, or R1° and R11 together form alkylene group
such as methylene group (-CHZ-), ethylene group (-CH2CH2-)
or propylene group (-CHZCH2CH2-).
Furthermore, in the case of n = m = 0, R15 and R12, or
R15 and R19 may be linked together to form a monocyclic or
polycyclic aromatic ring. Examples of the aromatic ring
which is formed with R15 and R1z in the case of n = m = 0,
include
_ (cH2)q- O _ (cHz)q o
0 0
0
_ ~ ~HZ ) Q o 0
0
wherein q is the same as defined in the formula (II).
Cycloolefins represented by the above-mentioned
formula (I) or (II) include
bicyclo-2-heptene derivatives (bicyclohept-2-ene
derivatives),
tricyclo-3- decene derivatives,
2 0 tricyclo-3-undecene derivatives,
tetracyclo-3-dodecene derivatives,
pentacyclo-9-pentadecene derivatives,
CA 02328828 2001-O1-08
72932-176
19
pentacyclopentadecadienene derivatives,
pentacyclo-3-pentadencene derivatives,
pentaccylo-4-hexadecene derivatives,
pentacyclo-3-hexadecene derivatives,
hexacyclo-4-heptadecene derivatives,
heptacyclo-5-eicocene derivatives,
heptacyclo-4-eicocene derivatives,
heptacyclo-5-heneicocene derivatives,
octacyclo-5-dococene derivatives,
nonacyclo-5-pentacosene derivatives,
nonacyclo-6-hexacosene derivatives,
cyclopentadiene-acenaphthylene adducts,
1,4-methano-1,4,4a,9a-tetrahydrofluorene derivatives
and
1,4-methano-1,4,4a,5,10,10a-hexahydroanthoracene
derivatives.
Examples of the cycloolefins represented by the
formula (I) or (II) are as follows:
The bicyclo[2.2.1]hept-2-ene derivatives such as
2 0 I Bicyclo[2.2.1]hept-2-ene
(= norbornene)
CH3
5-Methylbicyclo[2.2.I)hept-2-ene
CA 02328828 2001-O1-08
72932-176
CH3
5,6-Dimethylbicyclo[2.2.1]-hept-
CH3
2-ene
CH3
1-Methylbicyclo[2.2.1]hept-2-ene
C2H5
5-Ethylbicyclo[2.2.1]hept-2-ene
nC4H9
5-n-Butylbicyclo[2.2.1]kept-2-ene
iC4H9
5-Isobutylbicyclo[2.2.1]hept-2-
ene
CH3
7-Methylbicyclo[2.2.1]hept-2-ene:
the tricyclo[4.3Ø125]-3-decene derivatives such as
Tricyclo [ 4 . 3 . 0 . 12 5 ] -3-
decene,
CA 02328828 2001-O1-08
21 '
CH3
2-Methyltricyclo
[ 4 . 3 . 0 . 12 5 ] -3-decene
5-Methyltricyclo
[ 4 . 3 . 0 .12 5 ] -3-decene ;
CH3
the tricyclo[4.4Ø12 5]-3-undecene derivatives such
as
Tricyclo [ 4 . 4 . 0 . 12 5 ] -3-
undecene
CH3
10-Methyltricyclo
[ 4 . 4 . 0 . 12 5 ] -3-undecene ;
the tetracyclo[9.4Ø12~5.1~~10]-3-dodecene derivatives
S such as
Tetracyclo [4 . 4 .0 . 12~ 5 . 1~. 10 ] _
3-dodecene,
CA 02328828 2001-O1-08
22
8-Methyltetracyclo
[ 4 . 9 . 0 . 12 ~ 5 .17. 10 J -3-dodecene
CH3
8-Ethyltetracyclo
[4.4Ø12~5..1~.10J-3-dodecene
C2H5
8-Propyltetracyclo
[4.4Ø12~5.1~~10~-3-dodecene
C3H7
8-Butyltetracyclo
[ 4 . 4 . 0 . 12 ~ S . 17. 10 J -3-dodecene
.-C4H9
CH3 8-Isobutyltetracyclo-
[4.4Ø12~5.1~~10]-3-dodecene
CH2CH
CH3
8-Hexyltetracyclo
(4.4Ø12~5.1~~10]-3-dodecene
C6H13
8-Cyclohexyltetracyclo-
[ 4 . 4 . 0 .12 ~ 5 .1~ ~ 10 ~ -3-dodecene
8-Stearyltetracyclo-
[ 4 . 4 . 0 . 12 ~ S . 17 ~ 10 J -3-dodecene
C18H37
CA 02328828 2001-O1-08
23
CH3
5,10-Dimethyltetracyclo-
[4 .4 .0 . 12~5, l~.lo] _3-dodecene
CH3
CH3 CH3
2,10-Dimethyltetracyclo-
[q,4.0,12,5,17,10]-3-dodecene
CH3
8,9-Dimethyltetracyclo-
[4 . 4 . 0 . 12~ S . 1~. 10 ] _3-dodecene
CH3
CH3
8-Methyl-9-ethyltetracyclo-
[4 . 4 . 0 . 12~ 5 . 1~. 10 ] -3-dodecene
C2H5
CH3 CH3
11,12-Dimethyltetracyclo-
[4 . 4 . 0 . 12~ 5 . 1~~ 10 ] -3-dodecene
CH3
CH3 2,7,9-Trimethyltetracyclo-
[4 . 4 .0 . 12~ 5. 1~~ 10] -3-dodecene
CH3
CA 02328828 2001-O1-08
24
CH3
C2H5 9-Ethyl-2,7-
dimethyltetracyclo-
[4.4Ø12~5.1~~10]_3-dodecene
CH3
CH3 i H3
CH2CH 9-Isobutyl-2,7-
dimethyltetracyclo-
CH3 [ 4 . 4 . 0 . 12~ 5 . 1~~ 10 ~ _3-dodecene
CHg
CH3 CH3
9,11,12-Trimethyltetracyclo-
CH3 [4.4Ø12~5.1~~10]-3-dodecene
CH3 CH3
9-Ethyl-11,12-
r C2H5 dimethyltetracyclo-
[ 4 . 4 . 0 . 12 ~ 5 . 1~. 10 ] _3-dodecene
CH3 CH3 CH
3
CH CH 9-Isobutyl-11,12-
2I dimethyltetracyclo-
CH3 [4 . 4 .0 . 12~ 5. 1~~ 10 ~ _3-dodecene
CH3
5,8,9,10-
CH3
Tetramethyltetracyclo-
CHg
[4.4Ø12~5.1~~ lo] _3-dodecene
CH3
CA 02328828 2001-O1-08
25
8-Ethylidenetetracyclo-
CHCH3 ( 4 . 9 . 0 .12. 5 .1.10 ] _3_dodecene
CHg 8-Ethylidene-9-
CH CHg methyltetracyclo-
(4, 4, 0, 12 ~5, 1.10] _3_dodecene
C2H5 S-Ethylidene-9-
ethyltetracyclo-
CHCHg (4 . 4 Ø 12.5. 1.10] _3_dodecene
CH ( CH3 ) 2 g-Ethylidene-9-
isopropyltetracyclo-
(q,q,0,12,5,1~,1oj_3_dodecene
CHCH3
C4H9 8-Ethylidene-9-
butyltetracyclo-
CHCH3 [4 , q . 0 . 12~ 5 . 1~, l0 ] _3-dodecene
8-n-Propylidenetetracyclo-
CHCH2CH3 ( q .~4 . 0 . 12. 5 . 1,10 j _3-dodecene
CHg 8-n-Propylidene-9-
methyltetracyclo-
(4.9 Ø 12.5. 1~.10j _3_dodecene
CHCH2CH3
. C~'HS 8-n-Propylidene-9-
ethyltetracyclo-
CHCH2CH3 Iq . 4 . 0 . 12~ 5 . 1~~ 10] _3-dodecene
CA 02328828 2001-O1-08
26
CH ( CH3 ) 2
8-n-Propylidene-9-
isopropyltetracyclo
CHCH2CH3 [4 .4 .0 . 12~ 5, l~~ to] _3-dodecene
CqHg g-n-Propylidene-9-
butyltetracyclo-
CHCHZCHg f 4 . 4 . 0 .12~ 5 .1~. to ] -3_dodecene
8-Isopropylidenetetracyclo-
C-CHg [ 4 . 4 . 0 . 12 ~ S . 1~ ~ Zo ] -3-dodecene
CH3
CH3
8-Isopropylidene-9-
methyltetracyclo-
C-CH3 [ 4 . 4 . 0 .12~ 5 . 1~. to ] -3-dodecene
CH3
C2Hs
8-Isopropylidene-9-
ethyltetracyclo-
i -CH3 ( 4 . 4 . 0 . 12~ 5 . 1~. 10 ] -3-dodecene
CH3
CH ( CH3 ) 2
8-Isopropylidene-9-
isopropyltetra-
C-CHg cyclo [4 .4 .0 . 12~ 5. 1~~ 10] _3_
dodecene
CH3
CA 02328828 2001-O1-08
27
8-Isopropylidene-9-
butyltetracyclo-
H3 [4 . 4 . 0 .12~ 5 . 1,10 ] _3_
dodecene;
CH3
8-Chlorotetracyclo-
[4.4Ø12~5.1~~1o]-3-dodecene
CQ
8-Bromotetracyclo-
[ 4 . 4 . 0 . 12~ 5 . 1~, 10 ] _3-dodecene
Br
8-Fluorotetracyclo-
[4 . 4 .0 . 12~ 5. 1~~ 10 ] _3-dodecene
F
C2
8,9-Dichlorotetracyclo-
[4 .4 .0 . 12~ 5. 1~~ lo] -3-dodecene
CQ
the pentacyclo[6.5.1.13~6.02~~.09.13]_4-pentadecene
derivatives such as.
Pentacyclo[6.5.1.13,6.p2,7
09,13]_4-pentadecene
CH3 CH3
1,3-Dimethylpentacyclo-
[6.5.1.13~6.02~~.09~13]-4_
pentadecene
CQHg
C-C
CA 02328828 2001-O1-08
28 .
CH3
1,6-Dimethylpentacyclo-
( 6. 5 . 1 .13. 6 . 02, 7 . 0g, 13~ _q_
pentadecene
v
CH3
CH3 C H3 14,15-Dimethylpentacyclo-
[6.5.1.13~6. 02~7.09~13~_4_
pentadecene;
the pentacyclo[7.4Ø12~5.19~12.08,13~_3_pentadecene
derivatives such as
Pentacyclo-
[7.4.0 . 12.5. 19.12.08.13 _3_
pentadecene
CH3
Methyl-substituted
pentacyclo
[7. 4 . 0 . 12.5. 19.12.08, 13~ _3_
pentadecene;
the pentacyclopentadecadiene compounds such as
S
Pentacyclo(6.5.1.13,6.02,7.
09,13)-4,10-pentadecadiene;
the pentacpclo [ 8 . 4 . 0 . 12~ 5 . 19, 12 . 08, 13 ~ _3_hexadecene
derivatives such as
CA 02328828 2001-O1-08
29 ,
-~ 2 1 14 13 12
3 11 Pentacyclo[8.4Ø12~5
19,i2,08,13~-3-hexadecene
4 10
6 7 8 9
CH3 11-Methylpentacyclo-
[8. 4 .0 . 12.5, 19, 12 , ~8.13~ _3_
hexadecene
C2Hg 11-Ethylpentacyclo-
[8.4Ø12~5.19,12,08,13~_3_
hexadecene
CH3 10,11-Dimethylpentacyclo-
[8.4Ø12~5.19,12,~8.13~_3_
CH3 hexadecene;
the pentacyclo[6.6.1.13~6.027.09~14]_4-hexadecene
derivatives such as
Pentacyclo-
[6, 6, 1, 13.6 02.7 09.14 _4_
hexadecene
CH3 CH3
1,3-Dimethylpentacyclo-
[6, 6, 1, 13.6 02.7 ~9.14~ _q_
hexadecene
CA 02328828 2001-O1-08
30
1,6-Dimethylpentacyclo-
[ 6, 6, I, I3. 6~ 02.7 09.14 _q-
hexadecene
CH3
CH3 CH3
15,16-Dimethylpentacyclo-
[ 6, 6, 1, 13.6 02.7 09.14 _q_
hexadecene;
the hexacyclo [ 6 . 6 . 1.13~ 6 .110, 13 . 02, 7 . Og, 14 ~ -4-
heptadecene derivatives such as
Hexacyclo-
[6 . 6 . 1 . 13. 6. I10, 13 . 02.7 . O9, 19]
-9--heptadecene
CH3
12-Methylhexacyclo-
[6.6.1.13.6.I10,13,02.7.09.14~
-4-heptadecene
C2Hs
12-Ethylhexacyclo-
[6.6.1.13.6.I10,13_02.7.09.14~
-9-heptadecene
. i H3
12-Isobutylhexacyclo-
CH2CH [ 6 . 6 . 1 . 13~ 6 . 110, 13 , 02, 7 . Og, 14 ~
-4-heptadecene
~l/ ~l/ C H 3
CA 02328828 2001-O1-08
31
CH3 CH3
1, 6, 10-Trimethyl-12-
CH2CH isobutylhexacyclo
[6.6.1.13~6.110,13,02,7.09.14
CHg -4-heptadecene;
CH3 CH3
the heptacyclo-5-eicosene derivatives such as
Heptacyclo[8.7Ø12~9.14~7
111, 17 .03, 8 .012, 16~ _5_
eicosene;
the heptacyclo [ 8 . 7 . 0 . 13~ 6 . 110, 17 . 112, 15 , 02, 7 .011, 16 ~ -q-
eicosene derivatives such as
Heptacyclo [ 8 . 7 . 0 . 13 6 . 110, 17
112, 15 . 02, 7 , 011, 16~ -q-eicosene
CH3 CH3 Demethyl-substituted
heptacyclo-
[8.7Ø13~6.110,17.112,15,
02, 7 . 011, 16~ _q-eicosene;
the heptacyclo-5-heneicosene derivatives such as
Heptacyclo[8.8Ø12~9.14~7.
111,18.p3,8,p12,17~_5_
heneicosene
CA 02328828 2001-O1-08
32
4 3 2 1 18 1~ 16 Heptacyclo
15 18.8Ø14~7.111,18,
113.16,03.8.012.17 _5_
6 8 1 1 14 heneicosene
7 9 11 13
CHg 15-Methylheptacyclo-
[8.8Ø14~7.111,18,113,16,
03, a , 012,17 ~ _5_heneicosene
Trimethyl-substituted-
heptacyclo
[8.8Ø147.111,18,
CH CH3 ~ 3 113,16,03,8,012,17_5_
heneicosene;
the octacyclo [ 8 . 8 . 0 . 12 ~ g . 14 ~ 7 . 111, 18 , 113, 16 , 03, 8 , 012,
17 ~ _
5-docosene derivatives such as
Octacyclo-
[8.8Ø12.9,14,7.111,18,113,16.
03, 8 , 012, 17 ~ _5-docosene
CH3 15-Methyloctacyclo-
[8.8Ø12,9,14~7.111,18,
113, 16. 03, 8 , 012, 17 ~ _5-docosene
C2H5 15-Ethyloctacyclo-
[8.8Ø12,9,14,7.111,18
113. 16 . 03, 8 . 012, 17 ~ -5_
docosene;
the nonacyclo [ 10 . 9 . 1 . 14~ 7 . 113, 20 , 115, 18 _ 02, 10 , 03, 8
012,21,014,19~_5_pentacosene derivatives such as
CA 02328828 2001-O1-08
33
Nonacyclo [ 10 . 9 . 1 . 14~ ~ , 113, 20 ,
115,18.02,10.03,8.012,21.
p19,19]_5-pentacosene
IH3 iH3 Trimethyl-substituted-
nonacyclo-
[10.9.1.14~~.113,20,
115,18.02,10.03,8.012,21,
CH3 p14,19] -5-pentacosene;
the nonacyclo [ 10 . 10 . 1 . 15 8 . 114, 21 . 116, 19 , 02, 11 , 04, 9 ,
013,22,015,20]-g-hexacosene derivatives such as
5 3 1 21 19 Nonacyclo[10.10.1.158.114,21
2 22 20 1g 116,19.02,11,04,9.013,22.
17 015,20] _6-hexacosene;
9 11 1
8 10 12 14 15 16
and furthermore,
1
2 a 5-Phenyl-bicyclo[2.2.1]hept-
2-ene
3 5
4
- 5-Methyl-5-phenyl-
bicyclo[2.2.1]-hept-2-ene
CH3
CA 02328828 2001-O1-08
34
5-Henzyl-bicyclo[2.2.1]hept-
CH2 ~ 2-ene
5-Tolyl-bicyclo[2.2.1]hept-
2-ene
CH3
5- (Ethylphenyl) -
i bicyclo[2.2.1]hept-2-ene
CHzCH3
5-(Isopropylphenyl)-
>iH3 bicyclo[2.2.1]-hept-2-ene
CH
CH3
5-(Biphenyl)-bicyclo[2.2.1]
hept-2-ene
5- ((3-Naphthyl) -
bicyclo[2.2.1]hept-2-ene
_ 5- (a-Naphthyl) -
bicyclo[2.2.1]hept-2-ene
0
CA 02328828 2001-O1-08
5-(Anthracenyl)-
bicyclo[2.2.1)hept-2-ene
5,6-biphenyl-bicyclo[2.2.1]
hept-2-ene
Cyclopentadiene-
acenaphthylene adduct
5
4a 5a 6 1, 4-Methano-1, 4, 4a, 9a-
tetrahydrofluorene
z
9a V 8a
1 9 8
1 10 9
l0a 9a
z a 1,4-Methano-1,9,4a,5,10,10a-
hexahydroanthracene
4a 5a
5 6
8-Phenyltetracyclo-
[4 . 9 .0 . 125 1~~ 10] -3-dodecene
S
8-Methyl-8-phenyl-tetracyclo
[4 . 4 .0 . 12~ 5. 1~.10~ -3-dodecene
CH3
CA 02328828 2001-O1-08
36
/~ 8-Benzyl-tetracyclo-
CHZ-(( )) [9.4Ø12~5.1~~10]-3-dodecene
8-Tolyl-tetracyclo-
[4 . 9 .0 . 12~ 5. 1.10] _3-dodecene
CH3
8-(Ethylphenyl)-tetracyclo-
[4.4Ø12~5.1~.10~_3-dodecene
CHzCH3
8-(Isopropylphenyl)
~H3 tetracyclo[4.4Ø12~5.1~.10]
CH -3-dodecene
I
CH3
8,9-biphenyl-tetracyclo
( U
[4.4Ø12~5~1~~10]-3-dodecene
8-(Biphenyl)-tetracyclo
[ 4 . 4 . 0 . 12~ 5 . 1~. 10 ] _3-dodecene
8- ((3-Naphthyl) -tetracyclo-
[4 . 4 . 0 . 12~ 5. 1~, 10] -3-dodecene
8- (oc-Naphthyl) -tetracyclo-
[4.4Ø12~5.1~.10]-3-dodecene
CA 02328828 2001-O1-08
37
0
8-(Anthracenyl)-tetracyclo-
[4.4Ø12.5,17.10~_3-dodecene
Adduct of (cyclopentadiene-
acenaphthylene adduct) and
cyclopentadiene
3 1 13 12
4 2 11,12-Benzo-pentacyclo-
[6.5.1.13~6.02~7.09~13)_
4-pentadecene
~
6 8 9 10 11
3 11,12-Benzo-
4 2 1 1413 12 pentacyclo
[6.6.1.13.6_02.7.0919)_
5 4-hexadecene
6 7 8 9 10 11
11-Phenyl-hexacyclo-
[6.6.1.13~6.027.09,14)_
4-heptadecene . .
2 1 1~ 16 15 14,15-Benzo-heptacyclo-
[8.7Ø12.9.14.7.111~17.03.8
012, 16 ~ _5-eicosene
6 g 10 12 14
7 9 11 13
The cycloolefins of the formulas (I) and (II) may be
prepared by Diels-Adler reaction of a cyclopentadiene with
a corresponding olefin.
CA 02328828 2001-O1-08
38
In the cycloolefin random copolymers, the cycloolefin
of the formula (I) or (II) is considered to form repeating
units represented by the following formula (I') or (II'):
Ris
Rib
Rm
R~~
" _
(I')
wherein m, n, q, R1-R18, Ra and Rb are each as defined in
the formula (I); or
Rie R19
Rls ~ Rm
I I
n
(Cg2) q ~ ~ R15
io
9 R1J ~ ~R1A
I
m
Rii Ri2
' (II' )
wherein m, n, p, q and R1-R19 are each as defined in the
formula (II) .
CA 02328828 2001-O1-08
39
These cycloolefins may be used singly or in
combination of two or more kinds.
As the diene (iii) Which is, if necessary, used for
preparing the cycloolefin random copolymer [A-1] and the
cycloolefin random copolymer [B-1], non-conjugated dienes
of 5 to 20 carbon atoms represented by the following
formulas [III] to [VI] can be exemplified.
CHZ = CH - Y - CH = CHZ [III]
(Y is an alkylene group of 1 to 16 carbon atom)
(CH2) mCH=CHZ
L ~ n (IV]
(n = 0, 1 or 2; m is an integer of 0-11)
~ ~ n (Vl
(n = 0, 1 or 2)
( CHZ ) "
[vI]
(n is an integer of 1-6)
2 0 Exemplified as the non-conjugated diene represented by
the formula (III] may be 1,4-pentadiene, 1,5-hexadiene,
1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-
decadiene, 1,11-dodecadiene and 1,19-eicodiene.
CA 02328828 2001-O1-08
Exemplified as the diene represented by the formula
[IV] may be as in the following.
S-Vinyl-bicyclo[2.2.1]hept-2-ene (5-Vinyl-2-
S norbornene);
CH=CHz
5-Alyl-bicyclo[2.2.1]hept-2-ene;
CHZ-CH=CH2
5-(3-Hutenyl)-bicyclo[2.2.1]hept-2-ene;
CH2-CH2-CH=CH2
IS
8-Vinyl-tetracyclo[4.4Ø12~5.1~~10~_3-dodecene;
CH=CHz
2 0 and
11-Vinyl-hexacyclo [ 6 . 6 . 1 . 13~ 6 , 110, i3 . 02, 7 . 0 g, iq ] -4-
heptadecene;
CA 02328828 2001-O1-08
41
CH=CHZ
Exemplified as the non-conjugated diene represented by
the formula (V) may be as in the following,
Bicyclo[2.2.1)hept-2,5-diene (norbornadiene);
m
and
Tetracyclo[4.4Ø12~5,1~.10)-3,g-dodecadiene;
i i
Hexacyclo ['o . 6 . 1 . 13~ 6 , 110, 13 , 02, 7 . 09, 14 ) -4 ~ 11-
heptadecadiene;
i i
Exemplified as the non-conjugated diene represented by
2 0 the formula (VI) are the compounds as listed below.
1,1-Bis(5-bicyclo[2.2.1)hepta-2-enyl)methane;
I ~HZ i
CA 02328828 2001-O1-08
, 42
1,2-Bis(5-bicyclo[2.2.1]hepta-2-enyl)ethane;
CHZ-CHZ
and
1,6-Bis(5-bicyclo[2.2.1]hepta-2-enyl)hexane;
CHZ-CH2-CHZ-CHZ_CHZ_CHz --
In the non-conjugated dienes, hydrogen atoms attached
to carbon atoms other than those forming a carbon-carbon
double bond may be substituted with hydrocarbon radicals.
Of the dienes represented by the above formulas [III]
to [vI], 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, 5-
vinyl-bicycylo[2.2.1]hepto-2-ene, 8-vinyl-
tetracyclo[4.4Ø12~5.1~1°]-3-dodecene, bicyclo[2.2.1]hepto-
2, 5-dime and tetracyclo [4 . 4 . 0 . 12~ 5 . 1~~ 1°] -3, 8-dodecadiene
are preferably used.
In addition to the non-conjugated dienes represented
by the formulas (III) , (IV) , (V) and (VI) , also employable
as the diene (iii) in the invention are cyclic dienes, such
as 5-ethylidene-2-norbornene, 5-methylene-2-norbornene and
5-isopropylidene-2--norbornene.
These dimes can also be used singly or in combination
2 S of two or more kinds.
CA 02328828 2001-O1-08
43
The cycloolefin random copolymer [A-1] used for the
invention can be prepared by copolymerizing the Oc-olefin of
two or more carbon atoms (i) and at least one cycloolefin
(ii) represented by the aforesaid formula (I) or (II) and,
if necessary, the diene (iii) in the presence of a catalyst
(oc) formed from a soluble vanadium compound and an
organoaluminum compound (A), details of which will be
described below, or in the presence of a catalyst ((3)
formed from a metallocene compound of a transition metal
selected from Group IVB of the periodic table and
lanthanoid, and an organoaluminum oxy-compound and if
necessary an organoaluminum compound (B).
The soluble vanadium compounds forming the catalyst
(cc) may specifically be represented by the following
formula.
VO (OR) aVb or V (OR) ~Xd
where R is a hydrocarbon group, and a, b, c and d satisfy
relations of 0 <_ a <_ 3, 0 S b <_ 3,
<_ a+b <_ 3 , 0 <_ c <_ 4 , 0 <_ d <- 4 , and 3 _< c+d <_ 4 .
2 0 Examplss of the soluble vanadium compounds include
VOC13,
VO (OCZHS) C12,
VO (OCZHS) 2C1,
VO (O-iso-C3-H~) C12,
2 5 VO (O-n-C4H9) C12,
VO (OCZHS) 3, VOBr2, VC14, VOClz,
VO(O-n-C9H9)3 and
CA 02328828 2001-O1-08
44
VOC13 ~ 2 (OCeHI~OH) .
These compounds can be used singly or in combination
of two or more kinds.
The above mentioned soluble vanadium compound can be
used in the form of an electron donor addition product
thereof obtained by bringing an electron donor into contact
with the above-mentioned soluble vanadium compounds.
Such electron donors include, for example,
oxygen containing electron donors, such as alcohols,
1~ phenols, ketones, aldehydes, carboxylic acids, organic acid
halides, esters of organic or inorganic acids, ethers,
diethers, acid amides, acid anhydrides and alkoxysilanes,
and
nitrogen containing electron donors, such as ammonia
1S and ammonium salts, amines, nitriles, pyridines and
isocyanates;
more specifically,
alcohols having from 1 to 18 carbon atoms, such as
methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-
2 0 ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl
alcohol, bnenzyl alcohol, phenylethyl alcohol, cumyl
alcohol, isopropyl alcohol and isopropylbenzyl alcohol,
halogenated alcohols having from 1 to I8 carbon atoms,
such as trichloromethanol, trichloroethanol and
2 5 trichlorohexanol,
phenols having from 6 to 20 carbon atoms which may be
substituted with a lower alkyl group, such as phenol,
CA 02328828 2001-O1-08
cresol, xylenol, ethylphenol, propylphenol, nonylphenol,
cumylphenol and naphthol,
ketones having from 3 to 15 carbon atoms, such as
acetone, methylethyl ketone, methylisobutyl ketone,
5 acetophenone, benzophenone and benzoquinone,
aldehydes having from 2 to 15 carbon atoms, such as
acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde,
tolualdehyde and naphthaldehyde,
organic acid esters having from 2 to 18 carbon atoms,
10 such as methyl formate, methyl acetate, ethyl acetate,
vinyl acetate, propyl acetate, octyl acetate, cyclohexyl
acetate, ethyl propionate, methyl butyrate, ethyl valerate,
methyl chloroacetate, ethyl dichloroacetate, methyl
methacrylate, ethyl crotonate, ethyl cyclohexanecarbonate,
15 methyl benzoate, ethyl benzoate, propyl benzoate, butyl
benzoate, octyl benzoate, cyclohexyl benzoate, phenyl
benzoate, benzyl benzoate, methy toluylate, ethyl
toluylate, amyl toluylate, ethyl ethylbenzoate, methyl
anisate, ethyl anisate, ethoxy ethylbenzate, y-
2 0 butyrolactone, 8-valerolactone, cumarin, phthalide and
ethyl carbonate,
acid halides having from 2 to 15 carbon atoms, such as
acetyl chloride, benzoyl chloride, toluic acid chloride and
anisic acid chloride,
2 5 ethers having from 2 to 20 carbon atoms, such as
methyl ether, ethyl ether, isopropyl ether, butyl ether,
amyl ether, tetrahydrofuran, anisole and diphenyl ether,
CA 02328828 2001-O1-08
46
acid anhydrides, such as acetic anhydride, phthalic
anhydride and benzoic anhydride,
alkoxysilanes, such as ethyl silicate and
diphenyldimethoxysilane,
acid amides, such as acetic N,N-dimethylamide, benzoic
acid N,N-diethylamide and toluic acid N,N-dimethylamide,
amines, such as trimethylamine, triethylamine,
tributylamine, tribenzylamine and
tetramethylethylenediamine,
nitriles, such as acetonitrile and benzonitrile,
trinitrile, and
pyridines, such as pyridine, methylpyridine,
ethylpyridine and dimethylpyridine.
In the preparation of the electron donor addition
product of the soluble vanadium compound, the above-
exemplified electron donors may be used singly or in
combination of two or more kinds.
The organoaluminum compound (A) employable for the
catalyst (oc), which is used with the soluble vanadium
2 0 compound, includes a compound containing at least one A1-C
bond in the molecule. Examples of the organoaluminum
compounds include the compounds represented by the
following formulas (a) and (b).
(a) RlmA1 (OR2) ~HpXq
2 5 wherein each of R1 and RZ is a hydrocarbon group having
usually 1 - 15 carbon atoms, preferably 1 - 4 carbon atoms,
and they may be the same or different from each other; X is
CA 02328828 2001-O1-08
47
a halogen atom; m, n, p and q are numbers satisfying the
conditions of 0 <_ m <_ 3, 0 <_ n < 3, 0 <_ p < 3, 0 <_ q < 3,
and m+n+p+q = 3.
(b) M1A1R1q
wherein M1 is Li, Na or K; and R1 has the same meanings as
defined above.
Specific examples of the organoaluminum compounds
represented by the formula (a) include:
( 1 ) RlmA1 (ORz ) 3-m
wherein R1 and RZ have the same meanings as defined in the
formula (a), and m is preferably a number of
1.5 <_ m < 3;
( 2 ) RimAlX3_m
wherein R1 has the same meanings as defined in the formula
(a), X is halogen, and m is preferably a number of 0 < m <
3;
( 3 ) RlmAlH3_m
wherein R1 has the same meanings as defined in the formula
(a), and m is preferably a number of 2 <_ m < 3; and
2 0 ( 4 ) RlmA1 (ORZ ) nXq
wherein R1 and R2 have the same meanings as defined in the
formula (a), X is halogen, and m, n and q are numbers
satisfying the conditions of
0 < m <_ 3, 0 <_ n < 3, 0 5 q < 3, and m+n+q = 3 ,
More specifically, as these organoaluminum compounds
(A) of the formulas (1) to (4), the following compounds are
mentioned.
CA 02328828 2001-O1-08
48
The organoaluminum compounds of the formula (1)
include:
trialkylaluminum such as triethylaluminum and
tributylaluminum;
trialkenylaluminum such as triisopropenylaluminum;
dialkylaluminum alkoxide such as diethylaluminum
ethoxide and dibutylaluminum butoxide; and
ethylaluminum sesquiethoxide, butylaluminum
sesquibutoxide and partially alkoxylated alkylaluminum
1 0 represented for example by the formula Rl2.sA1 (OR2) o.s as an
average composition.
The organoaluminum compounds of the formula (2)
include:
dialkylaluminum halide such as diethylaluminum
chloride, dibutylaluminum chloride and diethylaluminum
bromide;
alkylaluminum sesquihalide such as ethylaluminum
sesquichloride, butylaluminum sesquichloride and
ethylaluminum sesquibromide; and
2 ~ partially halogenated alkylaluminum such as
ethylaluminum dichloride, propylaluminum dichloride and
butylaluminum dichloride.
The organoaluminum compounds of the formula (3)
include:
dialkylaluminum hydride such as diethylaluminum
hydride and dibutylaluminum hydride; and
CA 02328828 2001-O1-08
49
partially hydrogenated alkylaluminum such as
ethylaluminum dihydride and propylaluminum dihydride.
The organoaluminum compounds of the formula (4)
include:
partially alkoxylated and halogenated alkylaluminum
such as ethylaluminum ethoxychloride, butylaluminum
butoxychloride and ethylaluminum ethoxybromide.
Compounds similar to that represented by the formula
(a), for example, an organoaluminum compound in which two
or more aluminums are linked through oxygen atom or
nitrogen atom, may be used. Examples of such compounds
include:
(CZHS) ZAlOAl (CZHS) 2,
(CqH9) zAlOAl (CqH9) z and
1 S (CzHS) ZA1NA1 (CZHS) z.
CsHs
Further, the compounds belonging to the formula (b)
include LiAl(CZHS)q and LiAl(C~H15)q.
2 0 Among the above-exemplified organoaluminum compounds,
preferably used are alkylaluminum halide, alkylaluminum
dihalide and mixtures thereof.
Next, the catalyst ((3) formed from metallocene
compound of a transition metal selected from Group IVB of
2 5 the periodic table_or lanthanoids, organoaluminum oxy-
compound, and if neccessary, organoaluminum compound (B),
which is used in the copolymerization is explained.
CA 02328828 2001-O1-08
' S0
The metallocene compound of the transition metal
selected from Group IVB of the periodic table and
lanthanoids include the compounds represented by the
following formula (VII).
$ MLx ... (VII)
In the formula (VII), M is a transition metal selected
from Group IVB of the periodic table and lanthanoids, and
specific examples of M include zirconium, titanium,
hafnium, neodymium, samarium and ytterbium; L is a ligand
coordinating to the transition metal, and at least one of
the ligand L has a cyclopentadienyl skeleton; ligand L
other than that having a cyclopentadienyl skeleton is a
hydrocarbon group of 1-12 carbon atoms, an alkoxy group, an
aryloxy group, a halogen atom, a trialkylsilyl group, S03R
group (wherein R is a hydrocarbon group of 1 to 8 of carbon
atoms which may be a substituted, for example, with
halogen) or a hydrogen atom; and x is a valence of the
transition metal atom.
The ligands L having a cyclopentadienyl skeleton are,
2 0 for example, cyclopentadienyl group, alkyl-substituted
cyclopentadienyl groups such as methylcyclopentadienyl
group, dimethylcyclopentadienyl group,
trimethylcyclopentadienyl group,
tetramethylcyclopentadienyl group,
pentamethylcyclopentadienyl group, ethylcyclopentadienyl
group, methylethylcyclopentadienyl group,
propylcyclopentadienyl group, methylpropylcyclopentadienyl
CA 02328828 2001-O1-08
' S1
group, butylcyclopentadienyl group,
methylbutylcyclopentadienyl group, hexylcyclopentadienyl
group, or indenyl group, 4,5,6,7-tetrahydroindenyl group
and fluorenyl group. These ligands may be substituted with
a halogen atom or a trialkylsilyl group.
Among these ligands coordinating to the transition
metal, alkyl-substituted cyclopentadienyl groups are
particularly preferred.
When the compound of the above formula (VII) contains
at least two cyclopentadienyl groups, the two
cyclopentadienyl groups may be linked via an alkylene group
such as ethylene group or propylene group, an alkylidene
groups such as isopropylidene group, a susbtituted alkylene
group such as diphenylmethyl group, silylene group, or a
substituted silylene group such as dimethyl silylene group,
diphenylsilylene group or methylphenylsilylene group.
The ligands L other than those having a
cyclopentadienyl skeleton may include:
hydrocarbon group of 1-12 carbon atoms, specifically
2 0 alkyl group such as methyl group, ethyl group, propyl
group, isopropyl group and butyl group, cycloalkyl group
such as cyclohexyl group. aryl group such as phenyl group
and tolyl group, and aralkyl group such as neophyl group:
alkoxy group such as methoxy group, ethoxy group and
butoxy group;
aryloxy group such as phenoxy group;
CA 02328828 2001-O1-08
' S2
halogen atom such as fluorine, chlorine, bromine and
iodine;
ligand of the formula S03R such as p-toluenesulfonate
group, methanesulfonate group and trifluoromethanesulfonate
group.
When the valence of the transition metal atom M in the
formula (VII) is, for example, 4, the transition metal
compound of the formula (VII) may be represented, more
specifically, by the following formula (VII').
RlaRZbR3~R4dM ... (VII')
wherein M represents zirconium, titanium, hafnium,
neodymium, samarium or ytterbium, R1 represents a group
having a cyclopentadienyl skeleton, R2, R3 and R4 each
represent a group having a cyclopentadienyl skeleton, alkyl
1S group, cycloalkyl group, aryl group, aralkyl group, alkoxyl
group, aryloxy group, halogen atom, trialkylsilyl group,
S03R group or hydrogen atom, a is an integer of 1 or more,
and a+b+c+d=4.
In the present invention, there is used preferably a
2 0 transition metal compound having the above-mentioned
formula (VII') in which at least one of R2, R3 and R4 is
the group having a cyclopentadienyl skeleton, for example,
R1 and R2 are the groups having a cyclopentadienyl
skeleton. ~~The groups having a cyclopentadienyl skeleton
2 5 may be linked through an alkylene group such as ethylene or
propylene, an alkylidene group such as isopropylidene, a
substituted alkylene group such as diphenylmethylene,
CA 02328828 2001-O1-08
. 53
silylene group or a substituted silylene group such as
dimethylsilylene, diphenylsilylene or methylphenylsilylene.
Exemplified below are metallocene compounds of the
transition metal wherein M is zirconium.
Bis(indenyl)zirconium dichloride,
Bis(indenyl)zirconium dibromide,
Bis(indenyl)zirconium bis(p-toluenesulfonate),
Bis(9,5,6,7-tetrahydroindenyl)zirconium dichloride,
Bis(fluorenyl)zirconium dichloride,
1Q Ethylenebis(indenyl)zirconium dichloride,
Ethylenebis(indenyl)zirconium dibromide,
Ethylenebis(indenyl)dimethylzirconium,
Ethylenebis(indenyl)diphenylzirconium,
Ethylenebis(indenyl)methylzirconium monochloride,
15 Ethylenebis(indenyl)zirconium bis(methanesulfonate),
Ethylenebis(indenyl)zirconium bis(p-toluenesulfonate),
Ethylenebis(indenyl)zirconium
bis(trifluoromethanesulfonate),
Ethylenebis(4,5,6,7-tetrahydroindenyl)zirconium
2 ~ dichloride,
Isopropylidene(cyclopentadienyl-fluorenyl)zirconium
dichloride,
Isopropylidene(cyclopentadienyl-
methylcyclopentadienyl)zirconium dichloride,
2 5 Isopropylidene(cyclopentadienyl-
fluorenyl)dimethylzirconium,
CA 02328828 2001-O1-08
54
Dimethylsilylenebis(cyclopentadienyl)zirconium
dichloride,
Dimethylsilylenebis(methylcyclopentadienyl)zirconium
dichloride,
Dimethylsilylenebis(dimethylcyclopentadienyl)zirconium
dichloride,
Dimethylsilylenebis(trimethylcyclopentadienyl)-
zirconium dichloride,
Dimethylsilylenebis(indeny)zirconium dichloride,
Diemthylsilylenebis(indenyl)zirocnium
bis (trifluoromethanesulfonate) ,
Dimethylsilylenebis(4,5,6,7-
tetrahydroindenyl)zirconium dichloride,
Dimethylsilylenebis(cyclopentadienyl-
fluorenyl)zirconium dichloride,
Diphenylsilylenebis(indenyl)zirconium dichloride,
Methlphenylsilylenebis(indenyl)zirconium dichloride,
Bis(cyclopentadienyl)zirconium dichloride,
Bis(cyclopentadienyl)zirconium dibromide,
2 0 Bis(cyclopentadienyl)methylzirconium monochloride,
Bis(cyclopentadienyl)ethylzirconium monochloride,
Bis(cyclopentadienyl)cyclohexylzirconium monochloride,
Bis(cyclopentadienyl)phenylzirconium monochloride,
Bis(cyclopentadienyl)benzylzirconium monochloride,
2 5 Bis(cyclopentadienyl)zirconium monochloride
monohalide,
Bis(cyclopentadienyl)methylzirconium monohydride,
CA 02328828 2001-O1-08
5
Bis(cyclopentadienyl)dimethylzirconium,
Bis(cyclopentadienyl)diphenylzirconium,
Bis(cyclopentadienyl)dibenzylzirconium,
Bis(cyclopentadienyl)zirconium methoxy chloride,
Bis(cyclopentadienyl)zirconium ethoxy chloride,
Bis(cyclopentadienyl)zirconium bis(methanesulfonate),
Bis(cyclopentadienyl)zirconium bis(p-
toluenesulfonate).
Bis(methylcyclopentadienyl)zirconium dichloride,
Bis(dimethylcyclopentadienyl)zirconium dichloride,
Bis(dimethylcyclopentadienyl)zirconium ethoxy
chloride,
Bis(dimethylcyclopentadienyl)zirconium
bis(trifluoromethanesulfonate),
Bis(diemthylcyclopentadienyl)dimethylzirconium,
Bis(ethylcyclopentadienyl)zirconium dichloride,
Bis(methylethylcyclopentadienyl)zirconium dichloride,
Bis(propylcyclopentadienyl)zirconium dichloride,
Bis(methylpropylcyclopentadienyl)zirconium dichloride,
2 0 Bis(butylcyclopentadienyl)zirconium dichloride,
Bis(methylbutylcyclopentadienyl)zirconium
bis(methanesulfonate),
Bis(trimethylcyclopentadienyl)zirconium dichloride,
Bis(t.etramethylcyclopentadienyl)zirconium dichloride,
2 S Bis(pentamethylcyclopentadienyl)zirconium dichloride,
Bis(hexylcyclopentadienyl)zirconium dichloride, and
CA 02328828 2001-O1-08
56
Bis(trimethylsilylcyclopentadienyl)zirconium
dichloride.
In the transition metal compounds exemplified above,
the di-substituted cyclopentadienyl ring includes 1,2- and
1,3-substituted compounds, and the tri-substituted
cyclopentadienyl ring includes 1,2,3- and 1,2,4-substituted
compounds. Further, the alkyl group such as propyl or
butyl includes, for example, n-, i-, sec-, tert-isomers.
In the present invention, other transition metal
compounds in which the zirconium metal in the above-
exemplified compounds is replaced by titanium metal,
hafnium metal, neodymium metal, samarium metal or ytterbium
metal can also be used.
The organoaluminum oxy-compound, which is used for
forming the catalyst ((3) together with the above
metallocene compound of a transition metal selected from
Group IVB of the periodic table or lanthanoids, may be a
known aluminoxane, or may be a benzene-insoluble
organoaluminum oxy-compound.
2 0 The known a~.umino:cane may be specifically represented
by the following formula
RZA1 -f- OA1 -~- OAlRz
R
or
OA1 m+2
R
CA 02328828 2001-O1-08
57
wherein R is a hydrocarbon group such as methyl group,
ethyl group, propyl group or butyl group, preferably methyl
group or ethyl group, particularly methyl group, and m is
an integer of not less than 2, preferably an integer of 5
to 40.
In the above formulas, two or more of R may be
different from each other, that is, the aluminoxane may
comprise mixed alkyloxyaluminum units wherein two or more
of (OA1(R)) differ from each other.
The known aluminoxane may be prepared, for example, by
any one of the following processes, and is generally
obtained in the form of a solution in an aromatic
hydrocarbon medium.
(1) A process where an organoaluminum compound such
as trialkylaluminum is added to a suspension of a compound
containing adsorbed water, or a salt containing water of
crystallization such as magnesium chloride hydrate, copper
sulfate hydrate, aluminum sulfate hydrate, nickel sulfate
hydrate or cerous chloride hydrate, in an aromatic
2 0 hydroc.arben medium, to react them with each ether, and the
resulting aluminoxane is obtained in the form of a solution
in the aromatic hydrocarbon medium;
(2) A process where water, ice or steam is acted
directly on an ~ rganoaluminum compound such as
trialkylaluminum in a medium such as benzene, toluene,
ethyl ether or tetrahydrofuran, and the resulting
CA 02328828 2001-O1-08
aluminoxane is obtained in the form of a solution in the
medium used: and
(3) A process where an organoaluminum compound such as
trialkylaluminum is reacted with an organotinoxide such as
dimethyltinoxide and dibutyltinoxide in a solvent such as
decane, benzene or toluene.
used.
Of these processes, the process (1) is preferably
Specific examples~of the organoaluminum compounds
employable for preparing the solution of aluminoxane
include:
trialkylaluminums such as trimethylaluminum,
triethylaluminum, tripropylaluminum, triisopropylaluminum,
tri-n-butylaluminum, triisobutylaluminum, tri-sec-
1S butylaluminum, tri-tert-butylaluminum, tripentylaluminum,
trihexylaluminum, trioctylaluminum and tridecylaluminum;
tricycloalkylaluminums such as tricyclohexylaluminum
and tricyclooctylaluminum;
dialkylaluminum halides such as dimethylaluminum
2 0 chloride, diethylaluminum chloride, diethylaluminum bromide
and diisobutylaluminum chloride;
dialkylaluminum hydrides such as diethylaluminum
hydride and diisobutylaluminum hydride;
dialkylaluminum alkoxides such as dimethylaluminum
2 5 methoxide and diethylaluminum ethoxide; and
dialkylaluminum aryloxides such as diethylaluminum
phenoxide.
CA 02328828 2001-O1-08
59
_ Of these, trialkylaluminums are particularly
preferred.
Also employable as the organoaluminum compound is
isoprenylaluminum represented by the following formula:
S
(i-C9H9) xAly (CSHlo) z
wherein each of x, y and z is a positive integer, and z >_
2x.
The above-exemplified organoaluminum compounds may be
used singly or in combination.
The benzene-insoluble organoaluminum oxy-compound can
be obtained, for example, by bringing a solution of
aluminoxane into contact with water or an active hydrogen-
containing compound or by bringing the above-mentioned
organoaluminum compound into contact with water.
It is desirable to use the benzene-insoluble
organoaluminum oxy-compound in which, as is analyzed by
infrared spectrophotometry (IR), a ratio (DlZSO~Diz2o) of an
absorbance (Dlzso) at about 1250 cm-1 to an absorb ance (Dlz2o)
at about 1220 cm-1 is preferably not more than 0.09, more
preferably not more than 0.08, particularly preferably in
the range of 0.04 to 0.07.
The benzene-insoluble organoaluminum oxy-compound as
2 5 mentioned above is presumed to have an alkyloxyaluminum
unit represented by the following formula:
CA 02328828 2001-O1-08
R3
I
A1 - O -)--
wherein R3 is a hydrocarbon group of 1 to 12 carbon atoms.
Specific examples of the hydrocarbon group include methyl
5 group,.ethyl group, n-propyl group, isopropyl group, n-
butyl group, isobutyl group, pentyl group, hexyl group,
octyl group, decyl group, cyclohexyl group and cyclooctyl
group. Of these, preferred are methyl group and ethyl
group, and particularly preferred is methyl group.
10 In addition to the alkyloxyaluminum unit represented
by the above formula, the benzene-insoluble organoaluminum
oxy-compound may contain an oxyaluminum unit represented by
the following formula:
Rq
I
1 5 --f- A1 - o ~---
wherein R4 is a hydrocarbon group of 1 to 12 carbon atoms,
an alkoxy group of 1 to 12 carbon atoms, an aryloxy group
of 6 to 20 carbon atoms, a hydroxyl group, halogen or
2 0 hydrogen atom and is different from the group R3 in the
aforesaid formula.
In the case where the organoaluminum oxy-compound
contains the oxyaluminum unit, it is desirable that the
organoaluminum oxy-compound contains the alkyloxyaluminum
2 5 unit in an amount of not less than 30 ~ by mol, preferably
not less than 50 ~ by mol, more preferably not less than 70
by mol.
CA 02328828 2001-O1-08
61
By the term 'benzene-insoluble' organoaluminum oxy-
compound is meant that the compound is insoluble or
slightly soluble in benzene; the amount of A1 component
dissolving in benzene at 60°C is generally not more than 10
~, preferably not more than 5 % and particularly preferably
not more than 2 ~, in terms of A1 atom.
The organoaluminum oxy-compound used in the invention
may contain an organic compound component of other metals
than aluminum in a small amount.
As the organoaluminum compound (B) optionally used for
preparing the catalyst (p), there can be mentioned, for
example, an organoaluminum compound represented by the
following formula (VIII).
RSnAIX3_n . . _ (VIII)
wherein R5 is a hydrocarbon group of 1-12 carbon atoms, X is
halogen atom or hydrogen atom, and n is 1-3.
In the formula (VIII), RS is hydrocarbon group of 1-12
carbon atoms, such as, alkyl group, cycloalkyl group or aryl
group, including specifically methyl group, ethyl group, n-
2 0 propyl group, isopropyl group, isobutyl group, pentyl group,
hexyl group, octyl group, cyclopentyl group, cyclohexyl
group, phenyl group, tolyl group, etc.
The organoaluminum compounds (B) include, in
particular, compounds as mentioned below.
2 S Trialkylaluminum such as trimethylaluminum,
triethylaluminum, triisopropylaluminum, triisobutylaluminum,
trioctylaluminum, tri-2-ethylhexylaluminum, etc;
CA 02328828 2001-O1-08
62
alkenylaluminum such as isoprenylaluminum, etc;
dialkylaluminum halides such as dimethylaluminum
chloride, diethylaluminum chloride, diisopropylaluminum
chloride, diisobutylaluminum chloride, dimethylaluminum
bromide, etc;
alkylaluminum sesquihalides such as methylaluminum
sesquichloride, ethylaluminum sesquichloride,
isopropylaluminum sesquichloride, butylaluminum
sesquichloride, ethylaluminum sesquibromide, etc;
1~ alkylaluminum dihalides such as methylaluminum
dichloride, ethylaluminum dichloride, isopropylaluminum
dichloride, ethylaluminum dibromide, etc, and
alkylaluminum hydride such as diethylaluminum hydride
and diisobutylaluminum hydride.
As the organoaluminum compounds (B), there may also be
used a compound represented by the following formula (IX):
RSnAlY3_n ... (IX)
wherein RS is as defined above, Y is -OR6 group, -OSiR~3
group, -OAlRa2 group, -NR92 group, -SiRl~3 group, or
2 ~ -N (Ril) AiR122 group n is 1-2 and R°, R~, R8 and R1~ are each
methyl group, ethyl group, isopropyl group, isobutyl group,
cyclohexyl group, phenyl group, trimethylsilyl group, etc;
R9 is hydrogen atom, methyl group, ethyl group, isopropyl
group, phenyl gzoup, trimethylsilyl group, etc; and R1~ and
2 5 R11 are each methyl group, ethyl group, etc.
The organoaluminum compounds of the formula (IX)
include, in particular, such compounds as mentioned below.
CA 02328828 2001-O1-08
63
(i) Compounds of the formula RSnAl(OR6)3-n such as
dimethylaluminum methoxide,
diethylaluminum ethoxide,
diisobutylaluminum methoxide, etc;
(ii) Compounds of the formula RSnAl(OSiR~3)3-n such as
Et2A1(OSiMe3),
(iso-Bu)2A1(OSiMe3),
(iso-Bu)2A1(OSiEt3),etc;
(iii) Compounds of the formula R5nA1(OA1R82)3-n such as
Et2AlOAlEt2,
(iso-Bu)2A10A1(iso-Bu)z, etc;
(iv) Compounds of the formula R5nA1(NR92)3-n such as
Me2A1NEt2,
Et2AINHMe,
Me2AINHEt,
Et2AlN (SiMe3) 2.
(iso-Bu)2A1N(SiMe3)2, etc;
(v) Compounds of the formula R5nA1 (SiRl~3) 3-n such as
(iso-Bu)2AlSiMe3, etc; and
2 ~ (vi) Compounds of the formula R5nA1(N-A1R122)3-n such as
I
R11
Et2AINAlEt2, (iso-Bu)2A1NA1(iso-Bu)2, etc.
I
2 5 Me Et
Among the organoaluminum compounds represented by the
above formulas (VIII) and (IX), preferred are R53A1,
R5nA1(OR6)3-n and R5nA1(OA1R82)3-n~ Particularly preferred
are compounds in which R5 is isoalkyl group, and n is 2.
CA 02328828 2001-O1-08
64
These organoaluminum compounds may also be used in
combination of two or more kinds.
The ring-opening polymer [A-2] of a cycloolefin and
the ring-opening polymer (B-2] of a cycloolefin~both used
for the invention are each a ring-opening polymer of at
least one cycloolefin represented by the aforesaid formula
(I) or (II) .
Such ring-opening polymer of a cycloolefin can be
prepared by ring-opening polymerizing the cycloolefin of.
1~ the formula (I) or (II) alone or in combination in the
presence of a ring-opening polymerization catalyst.
Examples of the ring-opening polymerization catalyst
used herein include catalysts formed from halides of metals
such as ruthenium, rhodium, osmium, indium, platinum,
molybdenum and tungsten, nitrates of these metals, or
acetylacetone compounds of these metals, and reducing
agents such as alcohols and tin compounds; and catalysts
formed from halides of metals such as titanium, vanadium,
zirconium, tungsten and molybdenum, or acetylacetone
2 0 compounds of these metals, and metallic aluminum compounds.
In the preparation of the ring-opening polymer, other
cycloolefin than that of the above formula (I) or (II) may
be used in combination. Examples of other cycloolefin
include monocycIoolefins of 4 or more carbon atoms, such as
2 5 cyclobutene, cyclopentene, cyclooctene, cyclononene,
methylcyclopentene, methylcycloheptene, methylcyclooctene,
methylcyclononene, methylcyclodecene, ethylcyclopentene,
CA 02328828 2001-O1-08
ethylcycloheptene, ethylcyclooctene, ethylcyclononene,
dimethylcycloheptene, dimethylcyclooctene,
dimethylcyclononene, dimethylcyclodecene, cyclooctadiene
and cyclodecadiene; 2,3,3a,7a-tetrahydro-4,7-methano-1H-
5 indene; and 3a,5,6,7a-tetrahydro-4,7-methano-1H-indene.
Further, alkenes, such as propylene, 1-butene, 1-
pentene and 1-hexene, can be added as chain transfer agents
for molecular weight control.
In the ring-opening polymer, at least a part of the
IO cycloolefin represented by the aforesaid formula (I) is
assumed to have a structure represented by the following
formula (I-a), and at least a part of the cycloolefin
represented by the aforesaid formula (II) is assumed to
have a structure represented by the following formula (II-
1 5 a) .
Ris
Rib
Ri7
Ris
- (I-a)
wherein m, n, q, ql - R18, Ra and Rb have the same meanings
2 0 as defined in the aforementioned formula (I); and
CA 02328828 2001-O1-08
66
R18 Ri9
R16 ~ R17
n
(CHZ) q ~ ~ Ris
io
Rm ~ ~Ria
i
m
p Ril R12
(II-a)
wherein m, n, q, ql - R19, Ra and Rb have the same meanings
as defined in the aforementioned formula (II).
The hydrogenation product [A-3] of a ring-opening
polymer of a cycloolefin and the hydrogenation product [B-
3] of a ring-opening polymer of a cycloolefin both used for
the invention are each a hydrogenation product of a ring-
opening polymer of at least one cycloolefin represented by
the aforesaid formula (I) or (II).
Such hydrogenation product of a ring-opening polymer
of the cycloolefin can be obtained by hydrogenating the
cycloolefin ring-opening polymer as prepared above. For
hydrogenating the ring-opening polymer, a conventional
hydroganation process which is carried out in the presence
of a hydrogenation catalyst can be adopted.
As the hydrogenation catalyst, heterogeneous catalysts
or homogeneous catalysts, both of which are conventionally
used for the hydrogenation of olefin compounds, can be
2 0 employed. Particular examples of the heterogeneous
CA 02328828 2001-O1-08
67
catalysts include metals such as nickel, palladium and
platinum; and solid catalysts comprising these metals
supported on carriers such as carbon, silica, diatomaceous
earth, alumina and titanium oxide (e. g., nickel/silica,
nickel/diatomaceous earth, palladium/carbon,
palladium/silica, palladium/diatomaceous earth,
palladium/alumina). The homogeneous catalysts are, for
example, those based on metals of Group VIII of the
periodic table as substrates. Examples of such catalysts
include those formed from nickel compounds or cobalt
compounds and organometallic compounds of Groups I to III
metals of the periodic table, such as cobalt
naphthenate/triethylaluminum, cobalt octenate/n-butyl
lithium and nickel acetyiacetonate/triethylaluminum. Also
employable are Rh compounds.
The hydrogenation reaction using the above-described
hydrogenation catalyst can be carried out either in a
heterogeneous reaction system or in a homogeneous reaction
system according to the kind of the catalyst used. The
2 0 reaction in such system may be conducted in a hydrogen
atmosphere at a pressure of usually 1 to 150 atm and a
temperature of usually 0 to 180 °C, preferably 20 to 100
°C. The hydrogenation rate can be adjusted by
appropriately determining the reaction conditions such as
2$ hydrogen pressure, reaction temperature, reaction time and
catalyst concentration. In general, however, the reaction
conditions are selected in such a manner that the double
CA 02328828 2001-O1-08
' 68
bonds present in the main chain of the polymer is
hydrogenated in an amount of usually not less than 50 ~,
preferably not less than 80 ~, more preferably not less
than 90 ~, based on the whole amount of the double bonds.
In the hydrogenated cyclic polymer, at least a part of
the cycloolefin of the formula (I) is assumed to have a
structure represented by the following formula (I-b), and
at least a part of the cycloolefin of the formula (II) is
assumed to have a structure represented by the following
1 0 formula ( II-b) .
R~ Ril I
Ris
\ R16
R1~
Ris
'- Jn Rg ~ R12 Jm
(I-b)
wherein m, n, q, ql - R18, Ra and Rb have the same meanings
as defined in the aforementioned formula (I); and
CA 02328828 2001-O1-08
69
Rie Ris
1
Ris ~ Rm
i I
n
(CHZ) q ~ Ris
io
3 R13 ~ ~Rla
1
.-
R11 R12
P
(II-b)
wherein m, n, q, ql - Rlg, Ra and Rb have the same meanings
as defined in the aforementioned formula (II).
Now, the cycloolefin polymer [A] and the cycloolefin
polymer [B] for forming the cycloolefin polymer composition
of the invention are described below in more detail.
The cycloolefin polymer [A] for forming the
cycloolefin polymer composition of the invention is a
cycloolefin polymer selected from the group.consisting of
[A-1] the cycloolefin random copolymer, [A-2] the ring-
opening polymer of a cycloolefin and [A-3] the
hydrogenation product of a ring-opening polymer of a
cycloolefin, and the cycloolefin polymer [B] is a
cycloolefin polymer selected from the group consisting of
[B-1] the cycloolefin random copolymer, [B-2] the ring-
opening polymer of a cycloolefin and [B-3] the
hydrogenation product of a ring-opening polymer of a
cycloolefin, as described above.
CA 02328828 2001-O1-08
In the cycloolefin random copolymer [A-1], it is
desired that the recurring units derived from the a-olefin
component are contained in an amount of usually 60 to 97
by mol, preferably 70 to 95 % by mol; and the recurring
S units derived from the cycloolefin of the formula (I) or
(II) are contained in an amount of usually 3 to 40 % by
mol, preferably 5 to 30 % by mol. The diene compound is
desirably exist therein in an amount of not more than 10 %
by mol.
The intrinsic viscosity [~] of the copolymer [A-1], as
measured in decalin at 135 °C, is in the range of usually
D.5 to 5.0 dl/g, preferably 0.15 to 9.5 dl/g.
The glass transition temperature (Tg) of the copolymer
[A-1], as measured by DSC, is usually lower than 15 °C,
preferably in the range of -30 to 15 °C.
The refractive index np(A) of the copolymer [A-1], as
measured at 25 °C, is in the range of usually 1.500 to
1.650, preferably 1.510 to 1.600.
In the invention, the refractive index is a value
2 0 measured at 25 °C by the use of Abbe's refractometer (D-
lines, 589 nm).
The iodine value of the copolymer [A-1] is desirably
not more than 30 (g-iodine/100 g-polymer).
The intrinsic viscosity [~] of the ring-opening
copolymer (A-2] and the intrinsic viscosity (~] of the
hydrogenation product [A-3], as measured in decalin at 135
CA 02328828 2001-O1-08
7 1
°C, are each in the range of usually 0.5 to 5.0 dl/g,
preferably 0.15 to 4.5 dl/g.
The glass transition temperature (Tg) of the ring-
opening copolymer (A-2] and that of the hydrogenation
product [A-3], as measured by DSC, are each usually lower
than 15 °C, preferably in the range of -30 to 15 °C.
The refractive index no(A) of the ring-opening
copolymer [A-2] and that of the hydrogenation product [A-
3], as measured at 25 °C, are each in the range of usually
1.500 to 1.650, preferably 1.510 to 1.600.
The iodine value of the ring-opening copolymer (A-2]
and that of the hydrogenation product [A-3] are each
desirably not more than 30 (g-iodine/100 g-polymer).
In the cycloolefin random copolymer [B-1], it is
desired that the recurring units derived from the a-olefin
component are contained in an amount of usually 40 to 85 ~
by mol, preferably 92 to 80 g by mol; and the recurring
units derived from the cycloolefin of the formula (I) or
(II) are contained in an amount of usually 15 to 60 ~ by
2 0 mol, preferably 20 to 58 $ by mol. The diene compound is
desirably contained therein in an amount of not more than
10 ~ by mol.
The intrinsic viscosity (~] of the copolymer (B-1], as
measured in decalin at 135 °C, is in the range of usually
2 5 0.1 to 5.0 dl/g, preferably 0.15 to 4.5 dl/g.
CA 02328828 2001-O1-08
72
The glass transition temperature (Tg) of the copolymer
(B-1], as measured by DSC, is usually not lower than 70 °C,
preferably in the range of 90 to 200 °C.
The refractive index np(B) of the copolymer [B-1], as
measured at 25 °C ,is in the range of usually 1.500 to
1.650, preferably 1.510 to 1.600.
The iodine value of the copolymer [B-1] is desirably
not more than 30 (g-iodine/100 g-polymer).
The intrinsic viscosity [~] of the ring-opening
copolymer [B-2] and the intrinsic viscosity (~] of the
hydrogenation product (B-3], as measured in decalin at 135
°C, are each in the range of usually 0.1 to 5.0 dl/g,
preferably 0.15 to 4.5 dl/g.
The glass transition temperature (Tg) of the ring-
opening copolymer [B-2] and that of the hydrogenation.
product [B-3], as measured by DSC, are each usually not
lower than 70 °C, preferably in the range of 90 to 200 °C.
The refractive index np(B) of the ring-opening
copolymer (B-2] and that of the hydrogenation product [B-
2 0 3], as measured at 25 °C, are each in the range of usually
1.500 to 1.650, preferably 1.510 to 1.600.
The iodine value of the ring-opening copolymer [B-2]
and that of the hydrogenation product [B-3] are each
desirably not more than 30 (g-iodine/100 g-polymer).
The cycloolefin polymer composition of the invention
comprises the cycloolefin polymer [A] and the cycloolefin
polymer [B), and a difference Onp between the refractive
CA 02328828 2001-O1-08
73
index np(A) of the cycloolefin polymer [A] and the
refractive index np(B) of the cycloolefin polymer [B],
namely, lnp(A) - np(B)I, is not more than 0.015, preferably
not more than 0.012, more preferably not more than 0.010.
When the difference Onp between the refractive index
np(A) of the cycloolefin polymer [A] and the refractive
index no(B) of the cycloolefin polymer [B], that is, lno(A)
- np(B)I, exceeds 0.015, the resultant composition may be
sometimes deteriorated in the transparency.
Further, in the cycloolefin polymer composition of the
invention, a ratio of the cycloolefin polymer (A] to the
cycloolefin polymer (B] ([A]/[B], by weight) is in the
range of usually 8/92 to 90/60 (the total of [A] and [B] is
I00>, preferably 10/90 to 40/60.
The cycloolefin polymer composition as described above
can be prepared, for example, by the following processes.
(1) A process where the cycloolefin polymer [A] and
the cycloolefin polymer [B], both being separately
prepared, are mechanically blended by the use of an
2 0 extruder, a kneader, etc.
(2) A process where the cycloolefin polymer [A] and
the cycloolefin polymer (B], both being separately
prepared, are dissolved in a suitable solvent (e. g.,
saturated hydrocarbons such as heptane, hexane, decane and
cyclohexane; and aromatic hydrocarbons such as toluene,
benzene and xylene) to blend them (solution blending
process) .
CA 02328828 2001-O1-08
?4
(3) A multi-stage polymerization process where the
cycloolefin polymer [A] and the cycloolefin polymer [B) are
separately synthesized in a series of polymerization
reactors.
The cycloolefin polymer composition thus obtained has
a high transparency and is well-balanced among the
transparency, the heat resistance and the impact strength,
since the difference in the refractive index between the
cycloolefin polymer [A) and the cycloolefin polymer [B) is
1 0 small. -
The cycloolefin polymer composition of the invention
may be a radical reaction product of the cycloolefin
polymer [A) and the cycloolefin polymer [B) in the presence
of an organic peroxide and if necessary, a radical
polymerizable polyfunctional monomer.
The radical reaction product may be prepared by
radically reacting the cycloolefin polymer [A) and the
cycloolefin polymer [B) in the presence of an organic
peroxide and if necessary, a radical polymerizable
2 0 polyfunctional monomer.
Examples of the organic peroxide used herein include:
ketone peroxides, such as methyl ethyl ketone peroxide
and cyclohexanone peroxide;
peroxy ketals, such as 1,1-bis(tert-
2 5 butylperoxy)cyclohexane and 2,2-bis(tert-
butylperoxy)octane;
CA 02328828 2001-O1-08
72932-176
hydroperoxides, such as tert-butyl hydroperoxide,
cumene hydroperoxide, 2,5-dimethylhexane-2,5-
dihydroxyperoxide and 1,1,3,3-tetramethylbutyl
hydroperoxide;
5 dialkyl peroxides, such as di-tert-butyl peroxide,
2,5-dimethyl-2,5-di(tert-butylperoxy)hexane and 2,5-
diethyl-2,5-di(tert-butylperoxy)hexyne-3;
diacyl peroxides, such as lauroyl peroxide and benzoyl
peroxide; and
10 peroxy esters, such as tert-butyl peroxyacetate, tert-
butyl peroxybenzoate and 2,5-dimethyl-2,5-
di(benzoylperoxy)hexane.
Examples of the radical polymerizable polyfunctional
monomer, which is used if necessary, include divinylbenzene,
15 vinyl acrylate, vinyl methacrylate, triallyl isocyanurate,
diallyl phthalate, ethylene glycol dimethacrylate and
trimethylolpropane trimethacrylate.
In the preparation of the composition of the
invention, the radical reaction of the cycloolefin polymer
2 0 [A] with the cycloolefin polymer [B] in the presence of the
peroxide and if necessary, the radical polymerizable
polyfunctional monomer, may be prepared carried out in one
reactor. ,Otherwise, the composition of the present
invention may be prepared by the use of two or more than
2 S two reactors, wherein, for example, the cycloolefin polymer
[A] and the cycloolefin polymer [B] are radically reacted
in separate two or more reactors under different
CA 02328828 2001-O1-08
76
conditions, respectively, and each of the reaction mixtures
is blended together to obtain the composition of the
present invention.
In the radical reaction, the amount of the organic
peroxide used is in the range of usually 0.01 to 10 parts
by weight, preferably 0.05 to 5 parts by weight, based on
100 parts by weight of the total amounts of the cycloolefin
polymer [A] and the cycloolefin polymer [B]; and the amount
of the radical polymerizable polyfunctional monomer
optionally used is in the range of usually 0.01 to 15 parts
by weight, preferably 0.1 to 10 parts by weight, based on
100 parts by weight of the total amounts of the cycloolefin
polymer [A] and the cycloolefin polymer [B).
The radical reaction of the cycloolefin polymer [A]
with the cycloolefin polymer [B] is desirably conducted at
a temperature not lower than the decomposition temperature
of the organic peroxide. The reaction can be carried out
by mixing all the starting materials together, but it is
preferred that the cycloolefin polymer [A] is first mixed
2 0 with the cycloolefin polymer [B] to prepare a mixture to
which the organic peroxide and, if necessary, the radical
polymerizable polyfunctional monomer are then added to
react [A] and [B] with each other. The organic peroxide is
preferably added after the cycloolefin polymer [A) is
sufficiently mixed with the cycloolefin polymer [B].
Blending of the cycloolefin polymer [A] with the
cycloolefin polymer [B] can be carried out by various
CA 02328828 2001-O1-08
methods, for example, by mechanically blending the
cycloolefin polymer [A) and the cycloolefin polymer (B)
both having been separately prepared, in an extruder or the
like, by sufficiently dissolving the cycloolefin polymer
S (AJ and the cycloolefin polymer (B] in a suitable solvent
(e. g., saturated hydrocarbons such as heptane, hexane,
decane and cyclohexane; and aromatic hydrocarbons such as
toluene, benzene and xylene) to blend them (solution
blending method), and by separately synthesizing the
cycloolefin polymer [A] and the cycloolefin polymer (BJ in
different polymerization reactors and blending the
resulting polymers in a container.
To the mixture of the cycloolefin polymer [AJ and the
cycloolefin polymer (B] thus obtained, the organic peroxide
and if necessary, the radical polymerizable polyfunctional
monomer are added, and they are blended to react (AJ and
(B] at a temperature not lower than the decomposition
temperature of the organic peroxide.
The radical reaction may be carried out in a state
2 ~ where the mixture of the starting materials is molten,
namely, in the molten state, or may be carried out in a
state where the starting materials are dissolved in a
solvent, namely, in the solution state.
For conducting the radical reaction in the molten
2 5 state, the mixture of the starting materials can be mixed,
melted and 'reacted using a kneading apparatus such as a
mixing roll, a Banbury~~mixer, an extruder, a kneader or a
*Trade-mark
77
72932-176
CA 02328828 2001-O1-08
continuous mixer. This radical reaction is desirably
carried out at a temperature not lower than the temperature
at which a half-life period of the organic peroixde
corresponds to 1 minute, usually 15 to 300 °C, preferably
S 170 to 270 °C, and for a reaction time of usually 10 sec to
30 min, preferably 3 to 10 min.
As the solvent used for the radical reaction in the
solution state, there can be mentioned solvents similar to
those for the above-mentioned solution blending method.
This radical reaction is desirably carried out at a
temperature not lower than the temperature at which a half-
life period of the organic peroxide corresponds to 10
minutes, usually 50 to 300 °C, and for a reaction time of
usually 10 sec to 2 hours.
From the reaction product as obtained above is removed
the solvent by means of, for example, distillation, to
obtain the composition of the invention.
It is considered that the reason why the radical
reaction product composition exhibits much improved
2 0 transparency and impact resistance is that the organic
peroxide decomposes to produce radicals which cause the
radical reaction between the cycloolefin polymers [A] and
[B], whereby the cycloolefin polymers [A] and [B] are
partially bonded to each other with the intermolecular
2 5 chemical bonds.
When double bonds are present in the cycloolefin
polymer [A] and the cycloolefin polymer [B] or when
CA 02328828 2001-O1-08
79
constituent units derived from the radical polymerizable
polyfunctional monomer are present in the radical reaction
product, the bonding reaction may more easily take place,
and hence the resulting composition as a reaction product
which is further improved in the transparency and the
impact resistance can be obtained.
The first cycloolefin polymer composition and the
radical reaction modified product thereof according to the
invention can be used alone, or mixtures thereof with other
resins, particularly transparent resins, as far as
excellent properties of the composition and the radical
reaction modified product, particularly the transparency
and the impact resistance, are not deteriorated.
The second cycloolefin copolymer composition according
to the invention comprises a cycloolefin elastomer
component [Aa] and a cycloolefin copolymer componen t [Ba].
The cycloolefin elastomer component [Aa] is obtained by
2 0 copolymerizing (i) an cc-olefin of two or more carbon atoms
and (ii) a cycloolefin of the formula (I) or (II) , and
(iiia) a non-conjugated diene or 5 to 20 carbon atoms. The
cycloolefin copolymer component [Ba] is obtained by
copolymerizing the above Oc-olefin (i) and the above
2 5 cycloolefin (ii) in the presence of the cycloolef in
elastomer component [Aa] obtained above. In the second
cycloolefin copolymer composition of the invention, the
CA 02328828 2001-O1-08
cycloolefin elastomer component [Aaj has a polymerizable
carbon-carbon double bond, and hence it is assumed that the
cycloolefin elastomer component [Aa] and the cycloolefin
copolymer component [Ba] are chemically bonded in part as
described later.
The cycloolefin elastomer component [Aa] having a
polymerizable carbon-carbon double bond used for the
invention is described below in detail.
The cycloolefin elastomer component [Aa) used for the
invention is an elastomer having a polymerizable carbon-
carbon double bond, and is specifically a copolymer of (i)
an a-olefin of two or more carbon atoms, (ii) a cycloolefin
represented by the formula (I) or (II), and (iiia) a non-
conjugated diene of 5 to 20 carbon atoms.
Examples of the a-olefin of two or more carbon atoms
employable herein are the aforesaid a-olefins of 2 to 20
carbon atoms. They can be used singly or in combination of
two or more kinds. Of those, ethylene or propylene is
2 0 preferred.
Employable as the cycloolefin (ii) are cycloolefins
represented by the aforesaid formula (I) and/or (II), and
they can be used singly or in combination.
Employable as the non-conjugated diene of 5 to 20
2 5 carbon atoms (iiia) are specifically non-conjugated dienes
represented by the aforesaid formulas [III] to [VI], and
they can be also used singly or in combination.
CA 02328828 2001-O1-08
8I
Listed below are particular examples of the
cycloolefin elastomer component [Aa] having a polymerizable
carbon-carbon double bond.
The cycloolefin elastomer component [Aa] containing
units derived from the non-conjugated diene represented by
the formula [III] include:
ethylene/norbornene/1,5-hexadiene copolymer,
ethylene/5-methyl-2-norbornene/I,5-hexadiene copolymer,
ethylene/5-ethyl-2-norbornene/1,5-hexadiene copolymer,
IO ethylene/5-phenyl-2-norbornene/1,5-hexadiene copolymer,
ethylene/1,4-methano-1,4,4a,9a-tetrahydrofluorene/1,5-
hexadiene copolymer, ethylene/tetracyclododecene/1,5-
hexadiene copolymer,
ethylene/norbornene/1,7-octadiene copolymer,
ethylene/5-methyl-2-norbornene/1,7-octadiene copolymer,
ethylene/5-ethyl-2-norbornene/1,7-octadiene copolymer,
ethylene/5-phenyl-2-norbornene/1,7-octadiene copolymer,
ethylene/tetracyclododecene/1,7-octadiene copolymer,
ethylene/norbornene/1,9-decadiene copolymer,
2 0 ethylene/5-methyl-2-norbornene/1,9-decadiene copolymer,
ethylene/5-ethyl-2-norbornene/1,9-decadiene copolymer,
ethylene/5-phenyl-2-norbornene/1,9-decadiene copolymer,
ethylene/1,9-methano-1,4,4a,9a-tetrahydrofluorene/1,9-
decadiene copolymer and ethylene/tetracyclododecene/1,9-
2 5 decadiene copolymer.
CA 02328828 2001-O1-08
82
The cycloolefin elastomer component [Aa] containing
units derived from the non-conjugated diene represented by
the formula [IV) include:
_ ethylene/norbornene/5-vinyl-bicyclo[2.2.1]hept-2-ene
copolymer, ethylene/5-methyl-2-norbornene/5-vinyl-
bicyclo[2.2.1]hept-2-ene copolymer, ethylene/5-ethyl-2-
norbornene/5-vinyl-bicyclo[2.2.1)hept-2-ene copolymer,
ethylene/5-phenyl-2-norbornene/5-vinyl-bicyclo(2.2.1)hept-
2-ene copolymer, ethylene/1,4-methano-1,4,4a,9a- ,.
tetrahydrofluorene/5-vinyl-bicyclo(2.2.1)hept-2-ene
copolymer and ethylene/tetracyclododecene/5-vinyl-
bicyclo[2.2.1]hept-2-ene copolymer.
The cycloolefin elastomer component [Aa] containing
units derived from the non-conjugated diene represented by
the formula [V] include:
ethylene/norbornene/bicyclo[2.2.1]hept-2,5-diene
copolymer, ethylene/5-methyl-2-
norbornene/bicyclo[2.2.1)hept-2,5-diene copolymer,
ethylene/5-ethyl-2-norbornene/bicyclo[2.2.1)hept-2,5-diene
2 0 copolymer, ethylene/5-phenyl-2-
norbornene/bicyclo[2.2.1)hept-2,5-diene copolymer,
ethylene/1,4-methano-1,4,4a,9a-
tetrahydrofluorene/bicyclo[2.2.1)hept-2,5-diene copolymer,
ethylene/tetracyclododecene/bicyclo[2.2.1)hept-2,5-diene
2 5 copolymer,
ethylene/norbornene/tetracyclo[4.4Ø12.5.1~.10)_3~8-
dodecadiene copolymer, ethylene/5-methyl-2-
CA 02328828 2001-O1-08
83
norbornene/tetracyclo[4.4Ø12.5.1,10]-3,8-dodecadiene
copolymer, ethylene/5-ethyl-2-
norbornene/tetracyclo[4.4Ø12~5.1~~10)-3,8-dodecadiene
copolymer, ethylene/5-phenyl-2-
norbornene/tetracyclo[4.4Ø12.5.1,10]-3,8-dodecadiene
copolymer, ethylene/1,4-methano-1,4,4a,9a-
tetrahydrofluorene/tetracyclo[4.4Ø12~5.1~.10]-3~8-
dodecadiene copolymer and
ethylene/tetracyclododecene/tetracyclo[4.4Ø12~5.1~.10)_
3,8-dodecadiene copolymer.
The cycloolefin elastomer component (Aa] containing
units derived from the non-conjugated dime represented by
the formula [VI] include:
ethylene/norbornene/1,1-bis(5-bicyclo[2.2.1]hept-2-
enyl)methane copolymer, ethylene/5-methyl-2-norbornene/1,1-
bis(5-bicyclo[2.2.1]hept-2-enyl)methane copolymer,
ethylene/5-ethyl-2-norbornene/1,1-bis(5-bicyclo[2.2.1]hept-
2-enyl)methane copolymer, ethylene/5-phenyl-2-
norbornene/1,1-bis(5-bicyclo[2.2.1]hept-2-enyl)methane
2 0 copolymer, ethylene/1,4-methano-1,4,4a,9a-
tetrahydrofluorene/bis(5-bicyclo[2.2.1)hept-2-enyl)methane
copolymer and ethylene/tetracyclododecene/1,1-bis(5-
bicyclo[2.2.1)hept-2-enyl)methane copolymer.
The intrinsic viscosity [~) of the cycloolefin
2 5 elastomer component [Aa], as measured in decalin at 135°C,
is in the range of 0.5 to 5.0 dl/g, preferably 0.7 to 4.0
dl/g.
CA 02328828 2001-O1-08
In the cycloolefin elastomer component [Aa], it is
desired that the cycloolefin units are contained in an
amount of usually not less than 3 % by mol, preferably not
less than 5 % by mol.
5 The glass transition temperature (Tg) of the
cycloolefin elastomer component [Aa] is usually lower than
15 °C, preferably lower than 12 °C.
The iodine value of the cycloolefin elastomer
component [Aa] is in the range of usually 2 to 30 (g-
10 iodine/100 g-polymer), preferably 3 to 25 (g-iodine/100 g-
polymer) .
The refractive index np(Aa) of the cycloolefin
elastomer component [Aa] as measured at 25 °C is in the
range of usually 1.500 to 1.650, preferably 1.510 to 1.600.
15 Now, the cycloolefin copolymer component [Ba] is
described below in detail.
~vc ~ oo~ ef ~ n copo~yme~' ~'~mr~nnont ~Ba
The.cycloolefin copolymer component [Ba] is obtained
by copolymerizing (i) an a-olefin of two or more carbon
2 0 atoms and (ii) a cycloolefin in the presence of the above-
mentioned cycloolefin elastomer component [Aa] having a
polymerizable double bond.
As the Cc-olefin of two or more carbon atoms (i), those
exemplified before can be employed. Of those, ethylene or
25 propylene is preferred, and ethylene is particularly
preferred. Those oc-olefins can be used singly of in
combination or two or more kinds.
CA 02328828 2001-O1-08
1
-. Employable as the cycloolefin (ii) are specifically
cycloolefins represented by the aforesaid formula (I)
and/or (II), and they can be used singly or in combination.
The cycloolefin copolymer component [Ba] used for the
5 invention is an addition polymer obtained by polymerizing
the oc-olefin of two or more carbon atoms (i) and the
cycloolefin (ii) of the formula (I) or (II) in the presence
of the aforementioned cycloolefin elastomer component [Aa]
having a polymerizable double bond.
IO In the preparation of the cycloolefin copolymer
component [Ba], other cycloolefins than the cycloolefin of
the formula (I) or (II) can be additionally polymerized
together with the oc-olefin of two or more carbon atoms (i)
and the cycloolefin of the formula (I) or (II), with the
15 proviso that the properties of the copolymer component [Ba]
are not deteriorated.
The term "other cycloolefins" used herein has a wide
concept including unsaturated polycyclic hydrocarbon
compounds except the cycloolefin of the formula (I) or
20 (II) .
More specifically, as other cycloolefins, there can be
mentioned cyclobutene, cyclopentene, cyclohexane, 3,4-
dimethylcyclopentene, 3-methylcyclohexene, 2-(2-
methylbuty,l)-cyclohexene, styrene, oc-methylstyrene and
2 5 3a,5,6,7a-tetrahydro-4,7-methano-1H-indene.
rv~l ooh ef i n copol ~mpr ~ompo~
CA 02328828 2001-O1-08
86
The second cycloolefin copolymer composition according
to the invention comprises the cycloolefin elastomer
component [Aa] and the cycloolefin copolymer component
[Ba], and the cycloolefin elastomer component [Aa] is
S contained in the composition in an amount of 8 to 40 % by
weight, preferably IO to 35 % by weight.
In the cycloolefin copolymer composition of the
invention, a difference Ono between the refractive index
np(Aa) of the cycloolefin elastomer component [Aa] and the
refractive index no(Ba) of the cycloolefin copolymer
component [Ba] , namely, Inp (Aa) - np (Ba) I, is not more than
0.015. The cycloolefin elastomer component [Aa] is
preferably a copolymer of a cycloolefin represented by the
aforesaid formula (II), and the cycloolefin copolymer
component [Ba] is preferably a copolymer of a cycloolefin
represented by the aforesaid formula (I).
The cycloolefin copolymer composition of the invention
comprises the cycloolefin elastomer component [Aa] having a
polymerizable carbon-carbon double bond and the cycloolefin
2 0 copolymer component [Ba] obtained by copolymerizing the ct-
olefin of two or more carbon atoms (i) and the cycloolefin
(ii) in the presence of the cycloolefin elastomer component
[Aa], as described above, and in this composition, it is
assumed that the cycloolefin copolymer component [Ba]
formed from the Ct-olefin (i) and the cycloolefin (ii) and
the cycloolefin elastomer component [Aa] are chemically
bonded to each other at least in part. This is apparent
CA 02328828 2001-O1-08
w
from the fact that the cycloolefin copolymer composition of
the invention is superior in the transparency and the
impact resistance to a cycloolefin copolymer composition
which is obtained by simply blending the cycloolefin
elastomer component (Aa] and a cycloolefin random copolymer
component corresponding the component [Ba] which is
obtained by copolymerizing the Ct-olefin of two or more
carbon atoms (i) and the cycloolefin (ii) in the absence of
the cycloolefin elastomer component (Aa].
1~ It is assumed that this fact is brought about by that
the compatibility between the phase of the cycloolefin
copolymer component [Ba] and the phase of the elastomer
component [Aa] is further improved by the chemical bonds
which may be partially present between the (Aa) and the
1 5 (Ba] .
In the cycloolefin copolymer composition of the
invention, a difference Onp between the refractive index
np(Aa) of the cycloolefin elastomer component [Aa] and the
refractive index no(Ba) of the cycloolefin copolymer
2 0 component (Ba], namely, Inp(Aa) - no(Ba)I, is not more than
0.015 as described above, and it is preferably not more
than 0.12, more preferably not more than 0.010.
In this invention, the refractive index of the
cycloolefin elastomer component (Aa] and the refractive
2 5 index of the cycloolefin copolymer component (Ba] are
measured at 25 °C by the use of Abbe's refractometer (D-
lines, 589 nm).
CA 02328828 2001-O1-08
The cycloolefin copolymer component [Ba] herein. means
other portion than the cycloolefin elastomer component [Aa]
in the cycloolefin copolymer composition which is prepared
by copolymerizing the a-olefin (i) and the cycloolefin (ii)
in the presence of the elastomer component [Aa], but it is
impossible to separate the component [Ba] alone from the
composition by physical means, because a part of the
component [Ba] is chemically bonded to the elastomer
component [Aa].
Accordingly, the refractive index np(Ba) of the
component [Ba] herein is a value of refractive index np
measured on a cycloolefin random copolymer prepared from
the a-olefin (i) and the cycloolefin (ii) under the same
conditions as those for preparing the component [Ba] except
that the cycloolefin elastomer component [Aa] is not
present.
In the preparation of the cycloolefin elastomer
component (Aa] and the cycloolefin copolymer component
(BaJ~ there can generally be used a transition metal
2 0 catalyst, specifically
(a) a catalyst formed from a soluble vanadium compound
and an organoaluminum compound, or
(~) a catalyst formed from a metallocene compound of a
transition metal selected from Group IVB of the periodic
2 5 table and lanthanoid and an organoaluminum oxy-compound,
and if necessary, an organoaluminum compound.
CA 02328828 2001-O1-08
89
Details of the catalysts (a) and (~) are described
before in the preparation of the cycloolefin random
copolymers [A-lJ and [g-lj,
In this invention, the a-olefin of two or more carbon
atoms (i) is copolymerized with the cycloolefin (ii) in the
presence of the cycloolefin elastomer component [AaJ using
the above-mentioned catalyst (a) or (~) usually in a liquid
phase, preferably in a hydrocarbon solvent.
Examples of the hydrocarbon solvent include:
aliphatic hydrocarbons, such as pentane, hexane,
heptane, octane, decane, dodecane and kerosine, and halogen
derivatives thereof;
alicyclic hydrocarbons, such as cyclohexane,
methylcyclopentane and methylcyclohexane, and halogen
derivatives thereof; and
aromatic hydrocarbons, such as benzene, toluene and
xylene, and halogen derivatives thereof, such as
chlorobenzene.
In the copolymerization reaction, the liquid a-olefin
2 0 or the liquid cycloolefin per se can be used as the
solvent. A mixture of two or more of the solvents may also
be employed.
In the invention, the copolymerization reaction is
preferably conducted in the presence of any one of the
2 5 hydrocarbon solvents, preferably in the presence of a
mixture of these solvents. Particularly preferred solvent
mixtures are cyclohexane-hexane; cyclohexane-heptane,
CA 02328828 2001-O1-08
cyclohexane-pentane, toluene-hexane, toluene-heptane and
toluene-pentane.
The copolymerization can be carried out either
batchwise or continuously, but it is preferably carried out
5 continuously. The catalyst concentrations used are as
follows .
In the case of the catalyst (oc):
The soluble vanadium compound is fed to the
polymerization system in an amount of usually~0.01 to 5
IO mmol, preferably 0.05 to 3 mmol, per 1 liter of the
polymerization solution; and the organoaluminum compound is
fed to the polymerization system in such an amount that a
raio (A1/V) of the aluminum atom to the vanadium atom in
the polymerization system is not less than 2, preferably in
15 the range of 2 to 50, more preferably 3 to 20. In the
continuous copolymerization, the soluble vanadium compound
is fed to the system in a concentration of not more than 10
times, preferably 1 to 7 times, more preferably 1 to 5
times, as much as the concentration of the soluble vanadium
2 0 compound existing in the polymerization system.
In general, the soluble vanadium compound and the
organoaluminum compound are diluted with a liquid monomer
and/or the aforesaid hydrocarbon solvent followed by
feeding to~the Fsolymerization reactor. In this case, the
25 soluble vanadium compound is desirably diluted to the
above-mentioned concentration, while the organoaluminum
compound is desirably fed to the polymerization system
CA 02328828 2001-O1-08
91
after diluting it to a concentration of, for example, not
more than 50 times as much as the concentration thereof in
the polymerization system.
In the case of the catalyst
The metallocene compound is used in an amount of
usually about 0.00005 to 1.0 mmol, preferably about 0.0001
to 0.3 mmol, per 1 liter of the polymerization solution;
and the organoaluminum oxy-compound is used in such an
amount that the aluminum atom contained therein is in the
range of usually about 1 to 10,000 mol, preferably 10 to
5,000 mol, per 1 mol of the transition metal atom in the
metallocene compound.
The copolymerization reaction in the presence of the
catalyst (a) or (a) is generally carried out under the
conditions of a temperature of -50 to 200 °C, preferably -
30 to 150 °C, more preferably -20 to 100 °C, and a pressure
of more than 0 kg/cm2 to 50 kg/cm2, preferably more than 0
kg/cm2 to 20 kg/cm2. The reaction time (average residence
time in the continuous copolymerization) is varied
2 0 depending on various conditions such as kinds of the
monomers, catalyst concentrations and polymerization
temperatures, but is generally in the range of S minutes to
5 hours, preferably 10 minutes to 3 hours.
In the copo-lymerization reaction in the presence of
2 5 the component [Aa], it is desired that the a-olefin of two
or more carbon atoms (i) and the cycloolefin (ii) are fed
to the polymerization system in such amounts that a molar
CA 02328828 2001-O1-08
_ 92 '
ratio (i)/(ii) is in the range of 10/90 to 90/10,
. preferably 10/90 to 50/50
In the copolymerization, a chain transfer agent such
as hydrogen can also be employed for molecular weight
S control.
Through the above-mentioned procedure, a solution
containing the cycloolefin copolymer composition which
comprises the cycloolefin elastomer component [Aa] and the
cycloolefin copolymer component [Ba].obtained by
copolymerizing the oc-olefin of two or more carbon atoms (i)
and the cycloolefin (ii) of the formula (I) or (II) in the
presence of the elastomer component [Aa]. In this
solution, the cycloolefin copolymer composition is
contained in a concentration of usually 10 to 500 g/liter,
preferably 10 to 300 g/liter. The cycloolefin copolymer
composition is obtained by processing the solution in the
conventional manner.
More specifically, in order to prepare the cycloolefin
copolymer composition of the invention, it is possible to
2 0 dissolve the cycloolefin elastomer component [Aa] having
been beforehand prepared, e.g., in the form of pellets or
elastomer bales, in a hydrocarbon solvent to give a
solution in which the oc-olefin of two or more carbon atoms
(i) and the cycloolefin (ii) are copolymerized. It is also
possible to first prepare the cyc;l~o.lerto tlnal:~mr:r:
component [Aa] and then copolymerize the oc-olefin of two or
more carbon atoms (i) and the cycloolefin (ii) in the
CA 02328828 2001-O1-08
93
resulting polymerization solution of component [Aa] in a
two-stage polymerization process.
The second cycloolefin copolymer composition of the
invention can be used alone or in combination with other
resins, particularly transparent resins, as far as
excellent properties of the composition, particularly the
transparency and the impact resistance, are not
deteriorated.
1~ The Third Gycl~~lPf;~ ro~ymer ompo~it;nn
The third cycloolefin copolymer composition according
to the present invention comprises a cycloolefin elastomer
component (Aa] and a cycloolefin copolymer component [Ba].
The cycloolefin elastomer component [Aa] is obtained by
copolymerizing (i) an a-olefin of two or more carbon atoms
and (ii) a cycloolefin of the formula (I) or (II); and the
the cycloolefin copolymer component [Ba] is obtained by
copolymerizing the a-olefin (i) and the cycloolefin (ii) in
the presence of the cycloolefin elastomer component (Aa].
2 ~ It is considered that in such cycloolefin copolymer
composition of the invention, the cycloolefin elastomer
component [Aa] and the cycloolefin copolymer component
[Ba] are highly compatible with each other.
First', the_cycloolefin elastomer component [Aa]
2 5 substantially having no polymerizable carbon-carbon double
bond, which is used for the invention, will be described
below.
CA 02328828 2001-O1-08
94
The cycloolefin elastomer component [AOC] used for the
invention is an elastomer substantially having no
polymerizable carbon-carbon double bond, and is
specifically a copolymer of (i) an oc-olefin or two or more
carbon atoms and (ii) a cycloolefin of the formula (I) or
(II) .
Examples of the a-olefin of two or more carbon atoms
(i) are the aforesaid oc-olefins of 2 to 20 carbon atoms,
and they can be used singly or in combination of two or
more kinds. Of these, preferred is ethylene or propylene.
Employable as the cycloolefin (ii) are cycloolefins
represented by the aforesaid formula (I) and/or (II). They
can be used singly or in combination of two or more kinds.
Examples of the cycloolefin elastomer component [AOC]
substantially having no polymerizable carbon-carbon double
band include:
ethylene/norbornene copolymer, ethylene/5-methyl-2-
norbornene copolymer, ethylene/5-ethyl-2-norbornene
2 0 copolymer, ethylene/5-propyl-2-norbornene copolymer,
ethylene/5-butyl-2-norbornene copolymer, ethylene/5-pentyl-
2-norbornene copolymer, ethylene/5-hexyl-2-norbornene
copolymer, ethylene/5-heptyl-2-norbornene copolymer,
ethylene/5-octy-1-2-norbornene copolymer, ethylene/5-nonyl-
2-norbornene copolymer, ethylene/5-decyl-2-norbornene
copolymer, ethylene-5-undecyl-2-norbornene copolymer,
ethylene/5-dodecyl-2-norbornene copolymer, ethylene/S-
CA 02328828 2001-O1-08
phenyl-2-norbornene copolymer, ethylene/1,4-methano-
1,4,4a,9a-tetrahydrofluorene copolymer, and
ethylene/tetracyclododecene copolymer;
ethylene/propylene/norbornene copolymer,
5 ethylene/propylene/5-ethylidene-2-norbornene copolymer,
ethylene/propylene/5-methyl-2-norbornene copolymer,
ethylene/propylene/5-ethyl-2-norbonrene copolymer,
ethylene/propylene/5-propyl-2-norbornene copolymer,
ethylene/propylene/5-butyl-2-norbornene copolymer,
10 ethylene/propylene/5-pentyl-2-norbornene copolymer,
ethylene/propylene/5-hexyl-2-norbornene copolymer,
ethylene/propylene/5-heptyl-2-norbornene copolymer,
ethylene/propylene/5-octyl-2-norbornene copolymer,
ethylene/propylene/5-nonyl-2-norbornene copolymer,
15 ethylene/propylene/5-decyl-2-norbornene copolymer,
ethylene/propylene/5-undecyl-2-norbornene copolymer,
ethylene/propylene/5-dodecyl-2-norbornene copolymer,
ethylene/propylene/5-phenyl-2-norbornene copolymer, and
ethylene/propylene/tetracyclododecene copolymer;
2 0 ethylene/1-butene/norbornene copolymer, ethylene/1-
butene/5-ethylidene-2-norbornene copolymer, ethylene/1-
butene/5-methyl-2-norbornene copolymer, ethylene/1-
butene/5-ethyl-2-norbornene copolymer, ethylene/1-butene/5-
propyl-2-norbornene copolymer, ethylene/1-butene/5-butyl-2-
2 5 norbornene copolymer, ethylene/1-butene/5-pentyl-2-
norbornene copolymer, ethylene/1-butene/5-hexyl-2-
norbornene copolymer, ethylene/1-butene/5-heptyl-2-
CA 02328828 2001-O1-08
96 '
- norbornene copolymer, ethylene/1-butene/5-octyl-2-
norbornene copolymer, ethylene/1-butene/5-nonyl-2-
norbornene copolymer, ethylene/1-butene/5-decyl-2-
norbornene copolymer, ethylene/1-butene/5-undecyl-2-
norbornene copolymer, ethylene/1-butene/5-dodecyl-2-
norbornene copolymer, ethylene/1-butene/5-phenyl-2-
norbornene copolymer, and ethylene/1-
butene/tetracyclododecene copolymer;
ethylene/1-hexene/norbornene copolymer, ethylene/1-
hexene/5-methyl-2-norbornene copolymer, ethylene/1-
hexene/5-ethyl-2-norbornene copolymer, ethylene/1-hexene/5-
propyl-2-norbornene copolymer, ethylene/1-hexene/5-butyl-2-
norbornene copolymer, ethylene/1-hexene/5-pentyl-2-
norbornene copolymer, ethylene/1-hexene/5-hexyl-2-
norbornene copolymer, ethylene/1-hexene/5-heptyl-2-
norbornene copolymer, ethylene/1-hexene/5-octyl-2-
norbornene copolymer, ethylene/1-hexene/5-nonyl-2-
norbornene copolymer, ethylene/1-hexene/5-decyl-2-
norbornene copolymer, ethylene/1-hexene/5-undecyl-2-
2 0 norbornene copolymer, ethylene/1-hexene/5-dodeceyl-2-
norbornene copolymer, ethylene/1-hexene/5-phenyl-2-
norbornene copolymer, and ethylene/1-
hexene/tetracyclododecene copolymer;
ethylene/1=octene/norbornene copolymer, ethylene/1-
2 5 octene/5-methyl-2-norbornene copolymer, ethylene/1-
octene/5-ethyl-2-norbornene copolymer, ethylene/1-octene/5-
propyl-2-norbornene copolymer, ethylene/1-octene/5-butyl-2-
CA 02328828 2001-O1-08
97
norbornene copolymer,ethylene/1-octene/5-pentyl-2-
norbornene copolymer,ethylene/1-octene/5-hexyl-2-
norbornene copolymer,ethylene/1-octyl/5-heptyl-2-
norbornene copolymer,ethylene/1-octene/5-octyl-2-
norbornene copolymer,ethylene/1-octene/5-nonyl-2-
norbornene copolymer,ethylene/1-octene/5-decyl-2-
norbornene copolymer,ethylene/1-octene/5-undecyl-2-
norbornene copolymer,ethylene/1-octene/5-dodeceyl-2-
norbornene copolymer,ethylene/1-octene/5-phenyl-2-
norbornene copolymer,and ethylene/1-
octene/tetracyclododecene
copolymer;
and
ethylene/1-decene/norbornene
copolymer,
ethylene/1-
decene/5-methyl-2-norbornene
copolymer,
ethylene/1-
decene/5-ethyl-2-norbornene
copolymer,
ethylene/1-decene/5-
propyl-2-norbornene
copolymer,
ethylene/1-decene/5-butyl-2-
norbornene copolymer,ethylene/1-decene/5-pentyl-2-
norbornene copolymer,ethylene/1-decene/5-hexyl-2-
norbornene copolymer,ethylene/1-decene/5-heptyl-2-
norbornene copolymer,ethylene/1-decene/5-octyl-2-
norbornene copolymer,ethylene/1-decene/5-nonyl-2-
norbornene copolymer,ethylene/1-decene/5-decyl-2-
norbornene copolymer,ethylene/1-decene/5-undecyl-2-
norbornene copolymer,ethylene/1-decene/5-dodeceyl-2-
norbornene copolymer,ethylene/1-decene/5-phenyl-2-
2 5 norbornene copolymer,and ethylene/1-
decene/tetr acyclododecene copolymer.
CA 02328828 2001-O1-08
98
The intrinsic viscosity [11] of the cycloolefin
elastomer component [Aa], as measured in decalin at 135 °C,
is in the range of 0.5 to 5.0 dl/g, preferably 0.7 to 4.0
dl/g.
In the cycloolefin elastomer component [Aa], it is
desired that the cycloolefin units are contained in an
amount of not less than 3 ~ by mol, preferably not less
than 5 ~ by mol.
The glass transition temperature (Tg) of the
cycloolefin elastomer component [ACC] is usually lower than
°C, preferably lower than 12 °C.
The refractive index np(Aa) of the cycloolefin
elastomer component [Act], as measured at 25 °C, is in the
range of usually 1.500 to 1.650, preferably 1.510 to 1.600.
IS Next, the cycloolefin copolymer component [Ba] will be
descried below.
Cvcloo~efin copolymer cnmoonpnt fBocl
The cycloolefin copolymer component [BOC] used for the
invention can be obtained by copolymerizing (i) an Cc-olefin
2 0 of two or more carbon atoms and (ii) a cycfoolefin in the
presence of the cycloolefin elastomer component [AOC]
substantially having no polymerizable double bond.
Examples of the a-olefin of two or more carbon atoms
(i) are the aforesaid a-olefins of 2 to 20 carbon atoms,
and they can be used singly or in combination of two or
more kinds. Of these, preferred is ethylene or propylene,
and more preferred is ethylene.
CA 02328828 2001-O1-08 --
99
Employable as the cycloolefin (ii) are specifically
cycloolefins of the aforesaid formula (I) and/or (II), and
they can be used singly or in combination of two or more
kinds.
The cycloolefin copolymer component [BOC] used for the
invention is an addition type polymer obtained by
polymerizing the a-olefin of two or more carbon atoms (i)
and the cycloolefin (ii) of the formula (I) or (II) in the
presence of the aforesaid cycloolefin elastomer component
[ACC] substantially having no polymerizable double bond.
In addition to the a-olefin of two or more carbon
atoms (i) and the cycloolefin (ii), other cycloolefins than
the cycloolefin of the formula (I) or (II) can be also
additionally polymerized in the cycloolefin copolymer
component [Ba], with the proviso that the properties of the
copolymer component [Ba] are not deteriorated.
The term "other cycloolefins" used herein has a wide
concept including unsaturated polycyclic hydrocarbon
compounds as described above. For example, the same
2 0 compounds as those employable for the synthesis of the
aforementioned cycloolefin copolymer component [Ba] can be
employed.
~ycloo~ ef ~ n con~,~rmer composit s nn
The cycloolefin copolymer composition according to the
2 5 invention comprises the cycloolefin elastomer component
[AOC] and the cycloolefin copolymer component [BCC], and the
cycloolefin elastomer component [ACt] is contained in the
CA 02328828 2001-O1-08
100
composition in an amount of 8 to 40 % by weight, preferably
to 35 % by weight.
In the cycloolefin copolymer composition of the
invention, a difference ~np between the refractive index
. 5 np(Aa) of the cycloolefin elastomer component (AOC] and the
refractive index nD(BOC) of the cycloolefin copolymer
component (Boc] , namely, Ino (Aa) - np (BCC) (, is not more than
0.015. The cycloolefin elastomer component [AOC) is
preferably a copolymer of a cycloolefin of the formula
10 (II), and the cycloolefin copolymer component [BOt] is
preferably a copolymer of a cycloolefin of the formula (I).
In this invention, the refractive index of the
cycloolefin elastomer component [Aa) and the refractive
index of the cycloolefin copolymer component [BCC] are
measured at 25 °C by the use of Abbe.'s refractometer (D-
lines, 589 nm).
The cycloolefin copolymer composition of the invention
comprises the cycloolefin elastomer component [AOC]
substantially having no polymerizable carbon-carbon double
2 0 bond and the cycloolefin copolymer component (BOC] obtained
by copolymerizing the oc-olefin of two or more carbon atoms
(i) and the cycloolefin (ii) in the presence of the
cycloolefin elastomer component (Aa], and in the
composition, the phase of cycloolefin elastomer component
2 5 [ACt] is finely dispersed in the phase of cycloolefin
copolymer component [Ba] formed from the a-olefin (i) and
the cycloolefin (ii). This is apparent from the fact that
CA 02328828 2001-O1-08
101
the cycloolefin copolymer composition of the invention is
superior in the transparency and the impact resistance to a
cycloolefin copolymer composition which is obtained by
simply blending the cycloolefin elastomer component [Aa]
S and a cycloolefin random copolymer component corresponding
to the component [Ba] obtained by copolymerizing the a
olefin of two or more carbon atoms (i) and the cycloolefin
(ii) in the absence of the cycloolefin elastomer component
[Aa).
In the cycloolefin copolymer composition of the
invention, a difference ~np between the refractive index
no(Aa) of the cycloolefin elastomer component [Aa] and the
refractive index np(Ba) of the cycloolefin copolymer
component [Ba] , namely, Inp (Aa) - no (Ba) I, is not more than
0.015 as described above, and it is preferably not more
than 0.12, more preferably not more than 0.010.
The cycloolefin copolymer component (Ba] herein means
other component than the component [Aa] in the cycloolefin
copolymer composition which is prepared by copolymerizing
2 0 the a-olefin (i) and the cycloolefin (ii) in the presence
of the cycloolefin elastomer component [Aa], but it is
difficult to measure the refractive index no(Ba) alone,
because the component [Ba] and the component [Aa] are
quite compatible with each other.
2 5 Accordingly, the refractive index np(Ba) of the
component [Ba] herein is a value of refractive index np
measured on a cycloolefin random copolymer prepared from
CA 02328828 2001-O1-08
102
the a-olefin (i) and the cycloolefin (ii) under the same
conditions as those for preparing the component [Ba] except
that the cycloolefin elastomer component [Aa] is not
present.
In the preparation of the cycloolefin elastomer
component [Aa] and the cycloolefin copolymer component
[Ba], there can generally be used a transition metal
catalyst, specifically
(a) a catalyst formed from a soluble vanadium compound
and an organoaluminum compound, or
a catalyst formed from a metallocene compound of a
transition metal selected from Group IVB of the periodic
table and lanthanoid and an organoaluminum oxy-compound,
and, if necessary, an organoaluminum compound.
Details of the catalysts (a) and (~) are described
before in the preparation of the cycloolefin random
copolymers [A-1] and [B-1].
The copolymerization of the a-olefin of two or more
carbon atoms (i) and the cycloolefin (ii) in the presence
2 0 of the cycloolefin elastomer component [Aa] using the
above-mentioned catalyst (a) or (~) is also usually carried
out in a liquid phase, preferably in a hydrocarbon solvent.
As the hydrocarbon solvent, those exemplified before
can be employed: Further, the liquid a-olefin or the
2 5 liquid cycloolefin per se can also be used as the solvent.
Examples of the solvent preferably used for the
copolymerization reaction in the presence of the component
CA 02328828 2001-O1-08
103
(Aa] are mixed solvents such as cyclohexane-hexane,
cyclohexane-heptane, cyclohexane-pentane, toluene-hexane,
toluene-heptane and toluene-pentane.
The copolymerization can be carried out either
batchwise or continuously, but it is preferably carried out
continuously. The catalyst concentrations used are as
w follows.
In the case of the catalyst (oc)
The soluble vanadium compound is fed to the
polymerization system in an amount of usually 0.01 to 5
mmol, preferably 0.05 to 3 mmol, per 1 liter of the
polymerization solution; and the organoaluminum compound is
fed to the polymerization system in such an amount that a
raio (R1/V) of the aluminum atom to the vanadium atom in
the polymerization system is not less than 2, preferably in
the range of 2 to 50, more preferably 3 to 20. In the
continuous copolymerization, the soluble vanadium. compound
is fed to the system in a concentration of not more than 10
times, preferably~~l to 7 times, more preferably 1 to 5
2 0 times, as much as the concentration of the soluble vanadium
compound contained in the polymerization system.
In general, the soluble vanadium compound and the
organoaluminum compound are diluted with a liquid monomer
and/or the aforesaid hydrocarbon solvent followed by
feeding to the polymerization reactor. In this case, the
soluble vanadium compound is desirably diluted to the
above-mentioned concentration, while the organoaluminum
CA 02328828 2001-O1-08
104
compound is desirably fed to the polymerization system
after diluting it to a concentration of, for example, not
more than 50 times as much as the concentration thereof in
the polymerization system.
In the case of the catalyst (~):
The metallocene compound is used in an amount of
usually about 0.00005 to 1.0 mmol, preferably about 0.0001
to 0.3 mmol, per 1 liter of the polymerization solution;
and the organoaluminum oxy-compound is used in such an
IO amount that the aluminum atom contained~therein is in the
range of usually about 1 to 10,000 mol, preferably 10 to
5,000 mol, per 1 mol of the transition metal atom in the
metallocene compound.
The copolymerization reaction in the presence of the
15 catalyst (a) or (~) is generally carried out under the
conditions of a temperature of -50 to 200 °C, preferably -
30 to 150 °C, more preferably -20 to 100 °C,~ and a pressure
of more than 0 kg/cmz to 50 kg/cmz, preferably more than 0
kg/cmz to 20 kg/cm2. The reaction time (average residence
2 0 time in the continuous copolymerization) is varied
depending on various conditions such as kinds of the
monomers, catalyst concentrations and polymerization
temperatures, but is generally in the range of 5 minutes to
hours, preferably 10 minutes to 3 hours.
25 In the copolymerization reaction in the presence of
the component [Aa], it is desired that the a-olefin of two
or more carbon atoms (i) and the cycloolefin (ii) are fed
CA 02328828 2001-O1-08
105
to the polymerization system in such amounts that a molar
ratio (i)/(ii) is in the range of 10/90 to 90/10,
preferably 10/90 to 50/50.
In the copolymerization, a chain transfer agent such
as hydrogen can also be employed for molecular weight
control.
Through the above-mentioned procedures, a solution
containing the cycloolefin copolymer composition which
comprises the cycloolefin elastomer component [AGC] and the
cycloolefin copolymer component [BOC] obtained by
copolymerizing the a-olefin of two or more carbon atoms (i)
and the cycloolefin (ii) of the formula (I) or (II) in the
presence of the elastomer component [ACC]. In this
solution, the cycloolefin copolymer composition is
contained in a concentration of usually 10 to 500 g/liter,
preferably 10 to 300 g/liter. The cycloolefin copolymer
composition is obtained by processing the solution in the
conventional manner.
More specifically, in order to prepare the cycloolefin
2 0 copolymer composition of the invention, it is possible to
dissolve the cycloolefin elastomer component [ACt] having
been beforehand prepared, e.g., in the form of elastomer
pellets or elastomer bales, in a hydrocarbon solvent to
give a solutiocT in which the Cc-olefin of two or more carbon
2 5 atoms (i) and the cycloolefin (ii) are copolymerized. It
is also possible to first prepare the cycloolefin elastomer
component [AOC] and then copolymerize the oc-olefin of two
CA 02328828 2001-O1-08
106
or more carbon atoms (i) and the cycloolefin (ii) in the
resulting polymerization solution of component [Aa] in a
series of two-stage polymerization process.
The third cycloolefin copolymer composition of the
present invention can be used alone or in combination with
other resins, particularly transparent resins, as far as
excellent properties of the composition, particularly the
transparency and the impact resistance, are not
deteriorated.
The first, second and third cycloolefin polymer
compositions of the invention can be each molded by
conventional molding processes, for example, extrusion'
molding, injection molding, blow molding and rotational
molding, by means of a single-screw extruder, a vented
extruder, a twin-screw extruder, a conical type twin-screw
extruder, a co-kneader, a Plastificator, a mixtruder, a
twin-screw conical extruder, a planetary screw extruder, a
gear extruder, a screwless extruder, etc.
2 0 The cycloolefin copolymer compositions according to
the invention may contain rubber components to further
improve the impact strength thereof and/or various
additives, for example, heat stabilizer, weathering
stabilizer, antistatic agent, anti-slip agent, anti-
2 5 blocking agent, antifogging agent, lubricant, pigment, dye,
natural oil, synthetic oil and wax, provided that the
object of the invention is not marred.
CA 02328828 2001-O1-08
107
Stabilizers may optionally be added include, for
example,
phenolic antioxidants such as tetrakis[methylene-3-
(3,5-di-t-butyl-4-hydroxyphenyl)-propionate]methane, alkyl
ester of p-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid
and 2,2'-oxamidobis[ethyl-3-(3,5-di-t-butyl-4-
hydroxyphenyl)]propionate;
aliphatic acid metal salts such as zinc stearate,
calcium stearate and calcium 12-hydroxystearate; and
aliphatic acid esters of polyhydric alcohols such as
glycerin monostearate, glycerin monolaurate, glycerin
distearate, pentaerythritol monostearate, pentaerythritol
distearate and pentaerythritol tristearate.
These stabilizers may be used singly or in
combination. One of the examples is a combination of
tetrakis[methylene-3-(3,5-di-t-butyl-4-
hydroxyphenyl)propionate]methane with zinc stearate or with
glycerin monostearate.
In the present invention, particularly preferred is
2 0 the use of the phenolic antioxidant and the aliphatic acid
ester of polyhydric alcohol in combination. The aliphatic
acid ester of polyhydric alcohol is preferably such an
ester in which the polyhydric alcohol having 3 or more
hydroxy groups is partly esterified. The aliphatic acid
2 5 esters of polyhydric alcohols include, specifically,
aliphatic acid esters of glycerin such as glycerin
monostearate, glycerin monolaurate, glycerin monomyristate,
CA 02328828 2001-O1-08
1
glycerin monopalmitate, glycerin distearate and glycerin
dilaurate; and aliphatic acid esters of pentaerythritol
such as pentaerythritol monostearate, pentaerythritol
monolaurate, pentaerythritol dilaurate, pentaerythritol
distearate and pentaerythritol tristearate. The phenolic
stabilizer is used in an amount of 0 to 10 parts by weight,
preferably 0 to 5 parts by weight, more preferably 0 to 2
parts by weight, based on 100 parts by weight of the
cycloolefin resin. The aliphatic acid ester of the
polyhydric alcohol is used in an amount of 0 to 10 parts by
weight, preferably 0 to 5 parts by weight, based on 100
parts by weight of the cycloolefin resin.
Further, the cycloolefin random copolymer compositions
of the invention may include, provided that the object of
the invention is not marred, fillers such as silica,
diatomaceous earth, alumina, titanium oxide, magnesium
oxide, pumice powder, pumice balloons, aluminum hydroxide,
magnesium hydroxide, basic magnesium carbonate, dolomite,
calcium sulfate, potassium titanate, barium sulfate,
2 0 calcium sulfite, talc, clay, mica, asbestos, glass fibers,
glass flakes, glass beads, calcium silicate,
montmorillonite, bentonite, graphite, aluminum powder,
molybdenum sulfide, boron fibers, silicon carbide fibers,
fibers of polymer obtained from a-olefin having 2 or more
2 5 carbon atoms, such as polypropylene fibers, polyester
fibers and polyamide fibers.
CA 02328828 2001-O1-08
109
EFFEGT OF TH~ TNVFNTTn~
The first cycloolefin polymer composition of the
present invention comprises two kinds of the cycloolefin
copolymers (A] and [B] having specially combined
properties, wherein a difference ono = Ino(A) _ no(B)I
between the refractive index no(A) of the cycloolefin
polymer (A] and the refractive index np(B) of the
cycloolefin polymer [B] is not more than O.OIS, so that
this composition is excellent in the impact resistance, the
transparency and the heat resistance, and has a good
balance of these properties.
The second cycloolefin copolymer composition of the
present invention comprises the cycloolefin elastomer
component [Aa] containing a polymerizable carbon-carbon
double bond and the cycloolefin copolymer component [Ba]
obtained by copolymerizing the a-olefin of two or more
carbon atoms (i) and the cycloolefin (ii) in the presence
of the elastomer component (Aa], wherein a difference ono =
Inp(Aa) - np(Ba)I between the refractive index no(Aa) of the
2 0 component [Aa] and the refractive index np(Ba) of the
component (Ba] is not more than 0.015, and the cycloolefin
elastomer component (Aa] and the cycloolefin copolymer
component ..[Ba] are also chemically bonded to each other at
least in part, so that the composition is improved
2 5 especially in the impact resistance without trading off its
transparency.
CA 02328828 2001-O1-08
11~
The third cycloolefin copolymer composition of the
present invention comprises the cycloolefin elastomer
component [Aa] substantially having no polymerizable
carbon-carbon double bond and the cycloolefin copolymer
component [Ba] obtained by copolymerizing the a-olefin of
two or more carbon atoms (i) and the cycloolefin (ii) in
the presence of the elastomer component [Aa], and therefore
the phase o.f cycloolefin elastomer component (Aa] is finely
dispersed in the phase of cycloolefin copolymer component
1~ [Ba]. Further, the difference in the refractive index
between the component [Aa] and the component [Ba] is as
small as not more than 0.015 in the composition. Hence,
the composition is improved especially in the impact
resistance without trading off its transparency.
The present invention will be further described with
reference to the following examples, but it should be
construed that the invention is in no way limited to those
2 0 examples.
Measurement of various properties and evaluation are
carried out according to the following methods.
(1) Intrinsic viscosity
The intrinsic viscosity [~] was measured in decalin
2 5 at 135 °C by the use of Ubbelohde viscometer.
(2) Glass transition temperature (Tg)
CA 02328828 2001-O1-08
The glass transition temperature (Tg) was measured at
a heating rate of 10 °C/min in a NZ atmosphere by the use
of DSC-220C from Seiko Electron Co., Ltd.
(3) Melt flow rate (MFR)
The melt flow rate (MFR) was measured at 260 °C under
a load of 2.16 kg in accordance with ASTM D1238.
'(4) Refractive index
The refractive index was measured at 25 °C by the use
of Abbe' s refractometer (D-lines, 589 nm) .
(S) Monomer composition in copolymer
The monomer composition ratio was measured by means of
13C-NMR .
(6) Iodine value
The iodine value was measured by the iodine
monochloride method in accordance with JIS K3331.
(~) Preparation of specimen
A specimen, was prepared using an injection molding
machine IS50EPN*trom Toshiba Kikai Co., Ltd. and a
prescribed mold for specimen under the following molding
2 0 conditions. After molding, the specimen was allowed to
stand for 98 hours at room temperature, followed by
measurement.
Molding conditions
Cylinder -temperature: 260 °C
2 5 Mold temperature : 60 °C
Injection pressure
*Trade-mark
111
72932-176
CA 02328828 2001-O1-08
lI2
primary/secondary: 1,000 / 800 kg/cmz
(8) Light transmittance
Light transmittance was measured using a pressed sheet
of 2 mm in thickness as a sample, with the use of a
spectrophotometer MPS-2000 from Shimadzu Seisakusho Co.,
Ltd., at a wavelength of 780 nm.
(9) Izod impact strength
The Izod~impact strength was measured in accordance
with ASTM D256.
1 0 Size of specimen: 5/2 x 1/8 x 1/2t inch (notched)
Test temperature: 23 °C
(10) Heat distortion temperature (HDT)
The heat distortion temperature (HDT) was measured in
accordance with ASTM D648.
Size of specimen: 5 x 1/4 x 1/2t inch
Load: 264 psi
Preparation of Copoly~~",
[Synthesis of copolymer (a))
2 0 Copolymerization of ethylene and
tetracyclo[4.4Ø1z-5.1~-1°]-3-dodecene (hereinafter
sometimes abbreviated to "TCD") was continuously carried
out usingra vanadium catalyst in the following manner.
A cyclohexane solution of TCD was continuously fed to
2 S a 1-liter glass polymerization reactor, equipped with a
stirring blade, at the top of the reactor so that the TCD
concentration in the reactor was 60 g/liter. Further, a
CA 02328828 2001-O1-08
72932-176
113
cyclohexane solution of VO(O~ethyl)ClZ,and a cyclohexane
solution of ethylaluminum sesquichloride (A1 (CzHS) l.SCll.s)
were continuously fed to the polymerization reactor at the
top thereof, respectively, so that the vanadium
concentration and the aluminum concentration in the reactor
were 0.5 mmol/liter and 4.0 mmol/liter, respectively.
Through bubbling tubes, ethylene, nitrogen and hydrogen were
continuously introduced into the polymerization system at
rates of 36.0 liters/hr, 35.0 liters/hr and 1.0 liter/hr,
respectively.
The copolymerization reaction was conducted while
keeping the polymerization system at 10 °C by circulating a
cooling medium through a jacket provided outside the
reactor. A polymer solution containing a copolymer
resulting from the above copolymerization reaction was
continuously withdrawn from the top of the reactor so that
a volume of the polymer solution in the reactor was
constantly 1 liter (i.e., the average residence time was
0.5 hour). To the polymer solution was added a mixture of
2 0 cyclohexane/isopropyl alcohol (1/1) to terminate the
polymerization reaction. Thereafter, the polymer solution
was contacted with an aqueous solution containing 5 ml of
concentrated hydrochloric acid in 1 liter of water in a
proportion of 1:1 with vigorous stirring by means of a
2 S homomixer, thereby allowing the catalyst residue to
transfer into the aqueous phase. After allowing the
contacted mixture to stand, the aqueous phase was removed
CA 02328828 2001-O1-08
114
by separation, and the polymer solution phase was washed
twice with distilled water to purify it and separated.
Then, the polymer solution thus purified and separated
was poured into acetone in an amount of 3 times as much as
the polymer solution with vigorous stirring to precipitate
a copolymer, and the solid portion was collected by
filtration and thoroughly washed with acetone. Further,
the solid portion was introduced into acetone so as to be
40 g/liter and extracted the unreacted TCD present in the
copolymer at a temperature of 60 °C for 2 hours. After the
extraction, the solid portion was collected by filtration
and dried at 130 °C and 350 mmHg for 12 hours in a nitrogen
atmosphere.
In the above-mentioned manner, an ethylene/TCD
copolymer (a) was obtained. This ethylene/TCD copolymer
had an intrinsic viscosity [~] of 0.53 dl/g, Tg of 140 °C,
a TCD content of 36.5 $ by mol, and an iodine value of 0.1
g-iodine/100 g. The results are shown in Table 1.
2 0 (Synthesis of copolymer (b)]
A 1-liter stainless steel autoclave was charged with
239 ml of toluene, 134 g of norbornene (hereinafter
sometimes.abbreviated to "NB") was fed at room temperature
in a nitrogen stream, and the content in the autoclave was
stirred for 5 minutes (NB concentration in the reactor: 335
g/1). Subsequently, ethylene was passed through the
reaction system at atmospheric pressure with stirring to
CA 02328828 2001-O1-08
115
lay the system in an ethylene atmosphere. Keeping the
internal temperature of the autoclave at 70 °C, ethylene
was fed to the autoclave so that the internal pressure
became 4 kg/cm2. After stirring for 10 minutes, a toluene
S solution containing ethylenebis(indenyl)zirconium
dichloride and methyl aluminoxan, which had been beforehand
prepared, was added to the system to initiate the
copolymerization reaction of ethylene and NB. At this
time, the concentration of ethylenebis(indenyl)zirconium
dichloride in the system was 0.10 mmol/liter, and the
concentration of methyl aluminoxane in the system was 20
mmol/liter.
During the copolymerization, ethylene was continuously
fed to the system to keep the internal pressure at 4
kg/cm2. After 20 minutes, isopropyl alcohol was added to
the system to terminate the polymerization reaction. After
release of the pressure, the polymer solution was taken out
from the autoclave, and contacted with an aqueous solution
of 5 ml of concentrated hydrochloric acid in 1 liter of
2 0 water in a proportion of 1:1 with vigorous stirring by
means of a homomixer, thereby allowing the catalyst residue
to transfer into the aqueous phase. After allowing the
contacted~fiixture to stand, the aqueous phase was removed
by separation, and the polymer solution phase was washed
twice with distilled water to purify it and separated.
Then, the polymer solution thus purified and separated
was poured into acetone in an amount of 3 times as much as
CA 02328828 2001-O1-08
116
the polymer solution with vigorous stirring to precipitate
a copolymer, and the solid portion (copolymer) was
collected by filtration and thoroughly washed with acetone.
Further, the solid portion was introduced into acetone so
as to be 40 g/liter and extracted the unreacted NB present
in the copolymer at a temperature of 60 °C for 2 hours.
After the extraction, the solid portion was collected by
filtration and dried at 130 °C and 350 mmHg for 12 hours in
a nitrogen stream.
In the above-mentioned manner, an ethylene/norbornene
copolymer (b) was obtained. This ethylene/norbornene
copolymer had an intrinsic viscosity [t~] of 0.60 dl/g, Tg
of 151 °C, a NB content of 47.0 o by mol, and an iodine
value of 0.2 g-iodine/100 g-polymer. The results are shown
in Table 1.
[Synthesis of copolymer (c)]
The procedure for synthesizing the copolymer (a) was
repeated except that ethylidene norbornene (hereinafter
2 0 sometimes abbreviated to "ENB") as a diene was additionally
fed so as to be a concentration of 0.9 g/liter, and
ethylene at a rate of 36.0 liters/hr, nitrogen at a rate of
35.0 liter.s/hr and hydrogen at a rate of 1.0 liter/hr were
fed, to synthesize a copolymer (c). The results are shown
2 5 in Table 1.
[Syntheses of copolymers (d) to (g)]
CA 02328828 2001-O1-08
72932-176
117
The procedure for preparing the copolymer (a) was
repeated except that 5-phenylbioycloj2.2.1]hept-2-ene
(hereinafter sometimes abbreviated to "PhBH") as a
cycloolefin in place of TCD, and ethylene, nitrogen,
hydrogen and PhBH were fed in amounts shown in Table 1, to
synthesize copolymers (d) to (g). The results are also
shown in Table 1.
[Synthesis of copolymer (h)]
The procedure for synthesizing the copolymer (a) was
repeated except that NB as a cycloolefin in place of TCD,
and ethylene, nitrogen, hydrogen and NH were fed in amounts
shown in Table 1, to synthesize a copolymer (h). The
results are also shown in Table 1.
[Synthesis of copolymer (i)]
The procedure for synthesizing the copolymer (d) was
repeated except that PhBH and ENB, and ehtylene, nitrogen
and hydrogen were fed in amounts shown in Table 1, to
2 0 synthesize a copolymer (i). The results are shown in Table
1.
400.0 g of pellets of the copolymer (e) (component
2 S [A]) and 1,600.0 g of pellets of the copolymer (a)
(component [B]) were weighed, and they were sufficiently
mixed with each other in a nitrogen atmosphere in a
CA 02328828 2001-O1-08
polyethylene bag, followed by purging with nitrogen for 2
hours. The resultant mixture wa-s melt blended by means of
a twin-screw extruder (BT~30 from Plastic Engineering
Institute) at a cylinder maximum temperature of 260 °C for
a residence time of 1 minute, and pelletized by a
pelletizer.
The pellets thus obtained were molded and evaluated.
The light transmittance of the sheet 2 mm of thickness was
75 %; the Izod impact strength was 7.1 kg~cm/cm; and the
heat distortion temperature (HOT) under a load of 264 psi
was 122 °C. The results are shown in Table 2.
The procedure of E;cample 1 was repeated except that
600.0 g of the pellets of the copolymer (e) (component [A))
and 1,400.0 g of the pellets of the copolymer (a)
(component [B)) were used. The results are shwon in Table
2.
2 0 The procedure of Example 1 was repeated except that
the copolymer (d) (component [A)) and the copolymer (b)
(component [B)) were used. The results are shwon in Table
2.
2 5 Fxam~le 4
*. Trade-mark
118
72932-176
CA 02328828 2001-O1-08
lI9
The procedure of Example 1 was repeated except that
the copolymer (b) as a component [B] were used. The
results are shown in Table 2.
Fxamnle 5
The procedure of Example 1 was repeated except that
500.0 g of the pellets of the copolymer (f) (component [A])
and 1,500.0 g of the pellets of the copolymer (a)
(component [B]) were used. The results are shown in Table
2.
The procedure of Example 1 was repeated except that
400.0 g of the pellets of the copolymer (g) (component [A])
and 1,600.0 g of the pellets of the copolymer (a)
(component [B]) were used. The results are shown in Table
2.
It was shown that when Tg of the component [A] was
outside the range defined in the claim, the impact strength
2 0 of the composition was low.
S~omg,a~atsve Example 2
The procedure of Example 1 was repeated except that
600.0 g of the pellets of the copolymer (g) (component [A])
2 5 and 1,400.0 g of the pellets of the copolymer (a)
(component [B]) were used. The results are shown in Table
2.
CA 02328828 2001-O1-08
I20
It was shown that when Tg of the component (A] was
outside the range defined in the claim, the impact strength
of the composition was low even if the amount of the .
component [A] was increased.
S
Comparative Ex mpl~ 3
The procedure of Example 1 was repeated except that
400.0 g of the pellets of the copolymer (h) (component [A))
and 1,600.0 g of the pellets of the copolymer (a)
IO (component [B)) were used. The results are shwon in Table
2.
It was shown that when .the difference in the
refractive index between the component [A] and the
component [B] was large, the transparency of the
IS composition was deteriorated.
Comoaratsve ExamDlA a
The procedure of Example 1 was repeated except that
400.0 g of the pellets of the copolymer (h) (ccmponent [A))
2 0 and 1,600.0 g of the pellets of the copolymer (b)
(component [B]) were used. The results are shown in Table
2.
It was shown that when the difference in the
refractive index between the component [A] and the
2 5 component [B] was large, the transparency of the
composition was deteriorated.
CA 02328828 2001-O1-08
121
Examgle 6
A 1-liter glass flask was charged with 3.0 g of the
copolymer (i) (component [A]) and 12.0 g of the copolymer
(c) (component [B)) in a dry nitrogen atmosphere, and
further 470 ml of orthodichlorobenzene was added. In order
to completely dissolve the copolymers, the mixture was
heated to 160 °C to give a polymer solution.
Separately, 0.15 g of Percumyl D available from Nippon
Oils & Fats Co., Ltd. (dicumyl peroxide, hereinafter
sometimes abbreviated to "DCP") was dissolved in 30 ml of
orthodichlorobenzene.
The solution of DCP was dropwise added to the polymer
solution over a period of 30 minutes with stirring at 160
°C to initiate the radical reaction. Thereafter, the
reaction was continued at 160 °C, and the heating was
stopped after the lapse of 2 hours from completion of the
dropwise addition of the perioxide solution, followed by
allowing to cool to room temperature.
Subsequently, the reaction solution was pcured into a
2 ~ large amount of acetone with vigorous stirring to
precipitate a reaction product. The white solid was
separated by filtration and washed with a large amount of
acetone to' remove the unreacted DCP residue. The solid was
collected by filtration and dried at 130 °C and 350 mmHg
2 5 for 12 hours in a nitrogen stream.
In the above-mentioned manner, a cycloolefin polymer
composition was obtained. This composition had a light
CA 02328828 2001-O1-08
122
transmittance of 8? ?s, Izod impact strength of S.1 kg~cm/cm
and a heat distortion temperature (HDT) of 120 °C. The
results are shown in Table 3.
Exa~le 7
The procedure of Example 6 was repeated except that
DCP was not used, to prepare a composition. The results
are shown in Table 3.
1 O Exam_~ 1~8
A 1-liter glass flask was charged with 3.0 g of the
copolymer (d) (component [A]) and 12.0 g of the copolymer
(b) (component [B]) in a dry nitrogen atmosphere, and
further 440 ml of orthodichlorobenzene was added. In order
to completely dissolve the copolymers, the mixture was
heated to 160 °C to give a polymer solution.
Separately, 0.15 g of DCP was dissolved in 30 ml of
orthodichlorobenzene, and 0.30 g of divinylbenzene
(hereinafter sometimes abbreviated "DVB~~, available from
2 0 Wako Junyaku K.K.) was dissolved in 30 ml of
orthodichlorobenzene, respectively.
The solution of DCP and the solution of DVB were
dropwise added to the above-obtained polymer solution over
a period of 30 minutes with stirring at 160 °C to initiate
2 5 the radical reaction. Thereafter, the reaction was
continued at 160 °C, and the heating was stopped after the
lapse of 2 hours from completion of the dropwise addition
CA 02328828 2001-O1-08
123
of the peroxide solution, followed by allowing to cool to
room temperature.
Subsequently, the reaction solution was poured into a
large amount of acetone with vigorous stirring to
precipitate a reaction product. The white solid was
separated by filtration and washed with a large amount of
acetone to remove the unreacted DCP and DVB residue. The
solid was collected by filtration and dried at 130 °C and
350 mmHg for 12 hours in a nitrogen stream.
The results are shown in Table 3.
400.0 g of pellets of the copolymer (e) (component
[A]), 1,600.0 g of pellets of the copolymer (a) (component
[B]), 4 g of Perhexyne 25B (trade name, hereinafter
sometimes abbreviated to "PH25B", available from Nippon
Oils & Fats Co., Ltd.) and 8. g of DVB were introduced into
a polyethylene bag, and they were sufficiently mixed in a
nitrogen atmosphere in the polyethylene bag, followed by
2 0 purging with nitrogen for 2 hours. The resultant mixture
was melt blended by means of a twin-screw extruder (BT-30
from Plastic Engineering Institute) at a cylinder maximum
temperature of 260 °C for a residence time of 1 minute, and
pelletized by a pelletizer. The pellets thus obtained were
2 5 molded and evaluated.
The results are shown in Table 3.
Table 1
CA 02328828 2001-O1-08
124
Cycloolefin Die ne Feed Rate Gas
of
(1/hr)
CopolymerKind fount Kind Amount EthyleneNitrogenHydrogen
(g/1) (g/1)
Compo-(a) TCD 60.0 - - 36.0 35.0 1.0
vent (b) NB 335.0 - - (press ure: kg/cm2)
4
(c) TCD 60.0 ENB 0.9 36.0 35.0 1.0
(d) PhBH 9.6 - - 30.0 9.0 1.0
compo-(e) PhBH 11.2 - - 30.0 9.0 1.0
vent ( f ) PhBH 11 - - 30 . 9 . 0 .
. 0 8 2
9
(A) (g) PhBH 25.5 - - 30.0 9.8 0.2
(h) NB 7.8 - - 30.0 9.0 1.0
(i) PhBH 13.1 ENB 0.6 30.0 9.5 0.5
Table 1 (continued)
Polymer Content Intrinsic Refract-
Concent-of Tg ViscosityIV ive
Copolymerration Cycloolefin
(C) 11 *1 Index
(g/1) (mold) (dl/g)
Compo- (a) 98.0 36.5 190 0.53 0.1 1.543
nent (b) 67.0 97.0 151 0.60 0.2 1.532
(c) 47.1 35.1 135 0.55 3.1 1.541
(d) ~ 23.8 5.5 -5 1.41 0.1 1.532
Compo- (e) 24.5 8.6 -? 0.93 0.1 1.538
vent (f) 24.8 12.1 1 1.38 0.1 1.541
(g) 27.1 18.3 29 0.91 0.1 1.552
(h) 24.5 12.9 -7 1.13 0.1 1.515
(i) 25.0 12.5 3 1.11 3.6 1.539
The copolymers (a) and (c) to (h) were synthesized using a
catalyst of VO (OEt) C12/AlEtl,5C11,5 (0. 5/4 .0 mM) .
The copolymer (b) was synthesized using a metallocene
catalyst of Et(Ind)2ZrC12 and MAO (0.1/20 mM/L).
*1: g-iodine/100 g-polymer.
CA 02328828 2001-O1-08
125
Table 2
ComponentComponent(p,) / Difference Light IzodHDT
(g) of Transmit-
(AJ (H] Refractive tance *2
(by weight)Index ,~np (%)
Ex. CopolymerCopolymer20/80
1
0.005 75 7 122
(e) (a) .
1
Ex CopolymerCopolymer
2
30/70 0. 005 73 51 121
. (e) (a) .3
Ex CopolymerCopolymer
. 20/80
3
(d) (b) 0 88 5.1 122
q CopolymerCopolymer
Ex
, (e) (b) 20/80 0.006 71 6.4 121
CopolymerCopolymer
Ex
5
. (f) (a) 25/75 0.002 85 17.2122
Comp CopolymerCopolymer
.
Ex. (g) (g) 20/80 0.009 73 1.8 122
1
Comp.CopolymerCopolymer
30/70 0.009 70
Ex. (g) (a) 1.8 120
2
Comp CopolymerCopolymer
.
Ex. (h) (a) 20/80 0.028 8 9.3 lI8
3
Comp.CopolymerCopolymer
Ex. (h) (b) 20/80 0.017 10 10.5121
4
*2: kg~cm/cm
CA 02328828 2001-O1-08
126
Table 3
Component [A] Component [B) [A)/[B1 Refractive
by weight Index Ono
Ex. 6 Copolymer (i) Copolymer (c) 20/80 0.002
Ex. 7 Copolymer (i) Copolymer (c) 20/80 0.002
Ex. 8 Copolymer (d) Copolymer (b) 20/80 0
Ex. 9 Copolymer (e) Copolymer (a) 20/80 0.005
Table 3 (continued)
Organic PeroxideCrosslinking Light Izod HDT
Assisting AgentTransmittance
Kind Amount'3 Kind Amount'3 (%)
*2 (
C)
Ex. DCP 1.0 none - 87 5.1 120
6
Ex. none - none - 75 3.9 122
7
Ex. DCP 1.0 DVB 2.0 89 5.3 119
8
Ex. PH25B 0.2 DVB 0.9 82 7.1 120
9
*2: kg~cm/cm
*3: g/100 g-polymer
(Preparation of Cycloolefin Elastomer Component [Aa])
In a 1-liter glass polymerization reactor equipped
with a stirring blade, a cycloolefin elastomer [Aa] having
a polymerizable- carbon-carbon double bond was prepared in
the following manner.
A cyclohexane solution containing 5-phenyl-
bicyclo[2.2.1]hepto-2-ene (PhBH) and 5-vinyl-2-norbornene
(VNB) were continuously fed to the polymerization reactor
CA 02328828 2001-O1-08
127
at a rate of 0.9 liter/hr so that the concentrations of
PhBH and VNB in the reactor were 10.0 g/liter and 2.0
g/liter respectively, and cyclohexane was also continuously
fed at a rate of 0.5 liter/hr. Further, to the reactor
were continuously fed, as catalysts, a cyclohexane solution
of VO(OCzHS)C12 at a rate of 0.7 liter/hr (the concentration
of vanadium to be fed at this time Was 2.86 times as much
as that of the vanadium present in the reactor) so that the
vanadium concentration in the reactor was 0.5 mmol/liter,
and a cyclohexane solution of isobutylaluminum
sesquichloride (A1 (CqH9) 1.5011.5) at a rate of 0 . 4 liter/hr
so that the aluminum concentration in the reactor was 4.0
mmol/liter. Furthermore, to the polymerization system were
fed ethylene at a rate of 20.0 liters/hr, nitrogen at a
rate of 10.0 liters/hr and hydrogen at a rate of 1.0
liter/hr, through bubbling tubes.
The copolymerization reaction was conducted while
keeping the polymerization system at 10 °C by circulating a
cooling medium through a jacket provided outside the
2 0 polymerization reactor. A polymer solution containing an
ethylene/PhBH/VNB copolymer resulted from the above
copolymerization reaction was continuously withdrawn from
the top of the reactor so that the amount of the polymer
solution in the reactor was constantly 1 liter (i.e., the
2 5 average residence time was 0.5 hour). To the polymer
solution was added a small amount of methyl alcohol to
terminate the polymerization reaction. Thereafter, the
CA 02328828 2001-O1-08
128
polymer solution was contacted with an aqueous solution
containing 5 ml of concentrated hydrochloric acid in 1
liter of water in a proportion of 1:1 with vigorous
stirring by means of a homomixer, thereby allowing to
transfer the catalyst residue into the aqueous phase.
After allowing the contacted mixture to stand, the aqueous
phase was removed by separation, and the polymer solution
phase was washed twice with distilled water to purify it
and separated. The polymer solution thus separated was
then poured into acetone in an amount of 3 times as much as
the polymer solution with vigorous stirring. Then, the
solid portion was collected by filtration, thoroughly
washed with acetone, and dried at 130 °C and 350 mmHg for
12 hours.
In the above-mentioned manner, an ethylene/PhBH/VNB
copolymer was obtained as a cycloolefin elastomer component
[Aa] in an amount of 40.0 g/hr, i.e., 20.0 g/liter. The
copolymer obtained had an ethylene content of 82.6 ~ by
mol; a PhHH content of 11.4 ~ by mol; an intrinsic
2 0 viscosity [~J of 2.05 dl/g; a glass transition temperature
(Tg), measured by DSC, of 2.0 °C; an iodine value of 13.2
g-iodine/100 g-polymer; and a refractive index np(Aa),
measured at 25 °C, of 1.5408.
Separately, the polymerization reaction was carried
2 5 out as mentioned above and a polymer solution was withdrawn
from the top of the reactor, and washed with an acidic
water and then pure water to remove the catalyst residue.
CA 02328828 2001-O1-08
129
To the polymer solution, magnesium sulfate anhydride in an
amount of 10 g per 1 liter of the polymer solution was
added, and the resulting mixture was shaken to remove water
contained in the polymer solution to obtain a polymer
solution, which was used for the polymerization reaction in
Example 10.
In a 1-liter glass polymerization reactor equipped
with a stirring blade, the copolymerization of ethylene and
tetracyclo[4.9Ø12~5.1'~1°]-3-dodecene (TCD) in the presence
of the cycloolefin elastomer component [Aa] having a
polymerizable carbon-carbon double bond was continuously
carried out in the following manner.
The water-removed polymer solution obtained in the
manner mentioned above, which contained the ethylene/5-
phenyl-bicyclo[2.2.1]hepto-2-ene (PhBH)/vinyl norbornene
(VNB) copolymer (['~]: 2.05 dl/g, iodine value: 13.2 g-
iodine/100 g-polymer, Tg: 2.0 °C), was continuously fed to
2 0 the reactor at a rate of 0.5 liter/hr so that the
concentration of the ethylene/PhBH/VNB copolymer in the
reactor was 6.9 g/liter. Further, to the reactor was
continuously fed a cyclohexane solution of TCD at a rate of
0.4 liter/hr so that the TCD concentration in the reactor
2 5 was 60.0 g/liter. Furthermore, to the reactor from its
top, were continuously fed, as catalysts, a cyclohexane
solution of VO(OC2H5)Clz at a rate of 0.7 liter/hr (the
CA 02328828 2001-O1-08
130
concentration of vanadium to be fed at this time was 2.86
times as much as that of the vanadium present in the
reactor) so that the vanadium concentration in the reactor
was 0.5 mmol/liter and a cyclohexane solution of
isobutylaluminum sesquichloride (Al (C4H9) 1_SC11.5) at a rate
of 0.4 liter/hr so that the aluminum concentration in the
reactor was 4.0 mmol/liter. Moreover, to the
polymerization system were fed ethylene at a rate of 30.6
liters/hr, nitrogen at a rate of 40.6 liters/hr and
1~ hydrogen at a rate of 0.85 liter/hr, through bubbling
tubes.
The copolymerization reaction was conducted while
keeping the polymerization system at 10 °C by circulating a
cooling medium through a jacket provided outside the
polymerization reactor. A polymer solution of the
ethylene/TCD copolymer composition containing the
ethylene/5-phenyl-bicyclo[2.2.1]hepto-2-ene (PhBH)/vinyl
norbornene (VNB) copolymer resulted from the above
copolymerization reaction was continuously withdrawn from
2 0 the top of the reactor so that the amount of the polymer
solution in the reactor was constantly 1 liter (i.e., the
average residence time was 0.5 hour). To the polymer
solution was added a small amount of methanol to terminate
the polymerization reaction. Thereafter, the polymer
2 5 solution was contacted with an aqueous solution containing
5 ml of concentrated hydrochloric acid in 1 liter of water
in a proportion of 1:1 with vigorous stirring by means of a
CA 02328828 2001-O1-08
131
homomixer, thereby allowing the catalyst residue to
transfer into the aqueous phase. After allowing the
contacted mixture to stand, the aqueous phase was removed
by separation, and the polymer solution phase was washed
twice with distilled water to purify it and separated.
Subsequently, the polymer solution thus purified and
separated was then poured into acetone in an amount of 3
times as much as the polymer solution with vigorous
stirring.' Then, the solid portion was collected by
filtration and thoroughly washed with acetone. Further,
the solid portion thus washed was introduced into acetone
so as to be 40 g/liter and extracted TCD present in the
polymer at a temperature of 60 °C for 2 hours. After the
extraction, the solid portion was collected by filtration
and dried at 130 °C and 350 mmHg for 12 hours in a nitrogen
stream.
In the above-mentioned manner, a cycloolefin copolymer
composition comprising the ethylene/5-phenyl-
bicyclo[2.2.1]hepto-2-ene (PhBH)/vinyl norbornene (VNB)
2 0 copolymer and the ethylene/TCD copolymer was obtained in an
amount of 52.4 g/hr, i.e., 26.2 g/liter. In the cooolvmPr
composition thus produced, the component [Aa) was contained
in an amount of 26.3 ~ by weight. The MFR of the copolymer
composition, as measured at 260 °C under a load of 2.16 kg,
2 5 was 2.2 g/10 min. The Tg of the ethylene/TCD copolymer
component [Ba) was 143 °C.
The results are shown in Table 4.
CA 02328828 2001-O1-08
132
The procedure of Example 10 was repeated to prepare
copolymer compositions except for varying the conditions to
those shown in Table 4, and various cycloolefin copolymers
as (Aa) components, such as ethylene/PhBH/VNB copolymers
and an ethylene/PhBH/1,9-decadiene (1,9-DD) copolymer.
The results are shown in Table 9.
A 1-liter stainless steel autoclave was charged with
239 ml of toluene and 7.8 g of the ethylene/PhBH/VNH
copolymer (intrinsic viscosity [~): 2.23 dl/g, iodine
value: 11.9 g-iodine/100 g-polymer, Tg: -5.0 °C) obtained
by "Preparation of Cycloolefin Elastomer Component (Aa)",
134 g of norbornene (NB) was fed at room temperature in a
nitrogen atmosphere, and the content in the autoclave was
stirred for 5 minutes. Subsequently, ethylene was passed
through the reaction system at ordinary pressure with
stirring to lay the system in an ethylene atmosphere.
2 0 Keeping the internal temperature of the autoclave at 70 °C,
ethylene was fed to the autoclave so that the internal
pressure was 4 kg/cm2. After stirring for 10 minutes, a
toluene solution containing ethylenebis(indenyl)zirconium
dichloride and methyl aluminoxan, which had been beforehand
prepared, was added to the system to initiate the
copolymerization reaction of ethylene and NB. At this
time, the concentration of ethylenebis(indenyl)zirconium
CA 02328828 2001-O1-08
133
dichloride in the system was 0.10 mmol/liter, and the
concentration of methyl aluminoxane in the system was 20
mmol/liter. During the polymerization, ethylene was
continuously fed to the system to keep the internal
pressure at 4 kg/cm2. After 20 minutes, isopropyl alcohol
was added to the system to terminate the polymerization
reaction. After release of the pressure, the polymer
solution was taken out of the autoclave, and contacted with
an aqueous solution of 5 ml of concentrated hydrochloric
acid in 1 liter of water in a proportion of 1:1 with
vigorous stirring by means of a homomixer, thereby allowing
the catalyst residue to transfer into the aqueous phase.
After allowing the contacted mixture to stand, the aqueous
phase was removed by separation, and the polymer solution
IS phase was washed twice with distilled water to purify it
and separated.
Then, the polymer solution thus purified and separated
was poured into acetone in an amount of 3 times as much as
the polymer solution with vigorous stirring to precipitate
2 0 a copolymer, and the solid portion (copolymer) was
collected by filtration and thoroughly washed with acetone.
Further, the solid portion was introduced into acetone so
as to be 4,0 g/liter and extracted the unreacted norbornene
(NB) present in the copolymer at a temperature of 60 °C for
2 5 2 hours. After the extraction, the solid portion was
collected by filtration and dried at 130 °C and 350 mmHg
for 12 hours in a nitrogen stream.
CA 02328828 2001-O1-08
134
In the above-mentioned manner, a cycloolefin copolymer
composition comprising the ethylene/5-phenyl-
bicyclo[2.2.1]hepto-2-ene (PhBH)/vinyl norbornene (VNB)
copolymer and the ethylene/NB copolymer was obtained. In
the copolymer composition thus produced, the component [Aa]
was contained in an amount of 25.7 % by weight. The MFR of
the copolymer composition, as measured at 260 °C under a
load of 2.16 kg, was 2.0 g/10 min. The Tg of the component
[Ba] was 141 °C.
The results are shown in Table 4.
Comparative Example 5
The procedure of Example 10 was repeated except that
the cycloolefin elastomer component [Aa] was not present.
The results are shown in Table 4.
CA 02328828 2001-O1-08
135
Table 4
Elastomer
Component
[Aa]
ExampleKind of [~] Ph-NB Tg RefractiveIodine Value
Elastomer Conten Index (g-iodine/
100 g-
(dl/g)(mold) (C) (nD)*2 polymer)
Ex. Ethylene 2.05 11.0 2.0 1.5408 13.2
10
PhBH-VNB
Ex. Ethylene' 1.99 13.2 7.7 1.5472 12.1
11
PhBH-VNB
Ex. Ethylene' 2.17 12.0 2.1 1.5450 5.0
12
PhBH-1.9DD
Ex. Ethylene 2.23 5.1 -5.01.5311 11.9
13
PhBH-VNB
Ex. Ethylene 2.23 5.1 -5.01.5311 11.9
14
PhBH-VNB
Comp.
Ex. Component
5 [Aa] was
not present
*2: Measured at 25°C
CA 02328828 2001-O1-08
13b
Table 9 (Continued)
Conditions
for Synthesis
of Component
[Ba] in
the presence
of Component
[Aa]*1
Example Kind of Concentration Feed Rate Added Amount
Cycloolefin of Cycloolefinof of [Aa]
Ethylene
(g/1) (1/hr) (g/1)
Ex. 10 TCD 60.0 30.6 6,g
Ex. 11 TCD 60.0 30.6 6_g
Ex. 12 TCD 60.0 30.6 6,g
Ex. 13 TCD 55.0 30.5 6.0
Ex. 14 NB 335.0 (pressure:7,8
4 kg/cm2)
Comp. TCD 60.0 30.6 0
Ex. 5
*1: Feed rate of nitrogen = 40.6 1/hr, Feed rate of
hydrogen = 0.85 1/hr.
In Example 14, neither nitrogen nor hydrogen was fed.
CA 02328828 2001-O1-08
137
Table 4 (Continued)
Physical
Properties
of
Copolymer
Composition
Ex. ContentTg Refractiv Refractive Izod Light MFR
of [Aa]of Index of Index Impact trans-
[Ba] (sa) Difference gtrength mittance(g/10
(wt$) between
(C) (nD)*2 [Aa] and (kg~cm/cm)($) min)
[Ba]
Ex.lO 26.3 143 1.5427 0.0019 23 89 2.2
E.11 25.9 140 1.5430 0.0042 11 89 3.0
Ex.l2 26.8 144 1.5418 0.0032 22 88 2.4
Ex.l3 24.9 132 1.5401 0.0090 12 86 2.6
Ex.l4 25.7 141 1.5329 0.0018 28 88 2.0
Comp. 0 149 1.5441 - 1 89 5.0
Ex.S
*2: Measured at 25°C
CA 02328828 2001-O1-08
138
(Preparation of Cycloolefin Elastomer Component [Act])
In a 1-liter glass polymerization reactor equipped
with a stirring blade, a cycloolefin elastomer [AOC] was
synthesized in the following manner.
A cyclohexane solution of 5-phenyl-
bicyclo[2.2.1]hepto-2-ene (PhBH) was fed to the
polymerization reactor at a rate of 0.4 liter/hr so that
the PhBH concentration in the reactor was 10.6 g/liter.
Further, to the reactor were continuously fed, as
catalysts, a cyclohexane solution of VO(OCZHS)C12 at a rate
of 0.5 liter/hr (the concentration of vanadium to be fed at
this time was 2.86 times as much as that of the vanadium
present in the reactor) so that the vanadium concentration
in the reactor was 0.5 mmol/liter, and a cyclohexane
solution of isobutylaluminum sesquichloride
(A1 (CqH9) i.sCll.s) at a rate of 0. 4 liter/hr so that the
aluminum concentration in the polymerizer was 4.0
mmol/liter. Furthermore, cyclohexane was also continuously
fed to the reactor at a rate of 0.5 liter/hr. Moreover, to
2 0 the polymerization system were fed ethylene at a rate of
20.0 liters/hr, nitrogen at a rate of 10.0 liters/hr and
hydrogen at a rate of 0.5 liter/hr, through bubbling tubes.
The copolymerization reaction was conducted while
keeping the polymerization system at 10 °C by circulating a
2 5 cooling medium through a jacket provided outside the
reactor. A polymer solution of an ethylene/PhBH copolymer
resulted from the above copolymerization reaction was
CA 02328828 2001-O1-08
139
continuously withdrawn from the top of the reactor so that
the amount of the polymer solution in the reactor was
constantly 1 liter (i.e., the average residence time was
0.5 hour). To the polymer solution was added a small
amount of methyl alcohol to terminate the polymerization
reaction. Thereafter, the polymer solution was contacted
with an aqueous solution containing 5 ml of concentrated
hydrochloric acid in 1 liter of water in a proportion of
1:1 with vigorous stirring by means of a homomixer, thereby
allowing the catalyst residue to transfer into the aqueous
phase. After allowing the contacted mixture to stand, the
aqueous phase was removed by separation, and the polymer
solution phase was washed twice with distilled water to
purify it and separated. The polymer solution thus
separated was then poured into acetone in an amount of 3
times as much as the polymer solution with vigorous
stirring. Then, the solid portion was collected by
filtration, thoroughly washed with acetone, and dried at
130 °C and 350 mmHg for 12 hours.
2 0 In the above-mentioned manner, an ethylene/PhBH
copolymer was obtained as a cycloolefin elastomer component
[Aa] in an amount of 40.0 g/hr, i.e., 20.0 g/liter. The
copolymer obtained had an ethylene content of 87.8 ~ by
mol; a PhBH content of 12.2 % by mol; an intrinsic
2 5 viscosity [~] of 1.91 dl/g; a glass transition temperature
(Tg), measured by DSC, of 2.4 °C; an iodine value of 0.2 g-
CA 02328828 2001-O1-08
140 .
iodine/100 g-polymer; and a refractive index np(AOC),
measured at 25 °C, of 1.5916.
Separately, the polymerization reaction was carried
out as mentioned above and a polymer solution was withdrawn
S from the top of the reactor, and washed with an acidic
water and then pure water to remove the catalyst residue.
To the polymer solution was added magnesium sulfate
anhydride in an amount of 10 g per 1 liter of the polymer
solution, and the resulting mixture was shaken to remove
water contained in the polymer solution to obtain a polymer
solution, which was used for the polymerization reaction in
Example 15.
Example 15
In a 1-liter glass polymerization reactor equipped
with a stirring blade, the copolymerization of ethylene and
tetracyclo [4 . 4 . 0 . 1z~5. l~.lo) _3_dodecene (TCD) in the presence
of the cycloolefin elastomer component [AOC) substantially
containing no polymerizable double bond was continuously
2 0 carried out in the following manner.
The water-removed polymer solution obtained in the
manner mentioned above, which contained the ethylene/PhBH
copolymer ([T)): 1.91 dl/g, iodine value: 0.2 g-iodine/100
g-polymer; Tg: 2.4 °C), was continuously fed to the reactor
2 5 at a rate of 0.5 liter/hr so that the concentration of the
ethylene/PhBH copolymer in the reactor was 6.9 g/liter.
Further, to the reactor was continuously fed a cyclohexane
CA 02328828 2001-O1-08
141
solution of TCD at a rate of 0.4 liter/hr so that the TCD
concentration in the polymerizer was 60.0 g/liter.
Furthermore, to the reactor from its top were continuously
fed, as catalysts, a cyclohexane solution of VO (OCzHS) C12 at
a rate of 0.7 liter/hr (the concentration of vanadium to be
fed at this time was 2.86 times as much as that of the
vanadium present in the reactor) so that the vanadium
concentration in the reactor was 0.5 mmol/liter and a
cyclohexane solution of isobutylaluminum sesquichloride
1 0 (A1 (CQH9) 1,SC11.5) at a rate of 0. 4 liter/hr so that the
aluminum concentration in the reactor was 4.0 mmol/Titer.
Moreover, to the polymerization system were fed ethylene at
a rate of 30.6 liters/hr, nitrogen at a rate of 40.6
liters/hr and hydrogen at a rate of 0.85 liter/hr, through
bubbling tubes.
The copolymerization reaction was conducted while
keeping the polymerization system at 10 °C by circulating a
cooling medium through a jacket provided outside the
polymerization reactor. A polymer solution of the
2 0 ethylene/TCD copolymer composition containing the
ethylene/PhBH copolymer resulted from the above
copolymerization reaction was continuously withdrawn from
the top of the reactor so that the amount of the polymer
solution i~n the_reactor was constantly 1 liter (i.e., the
2 5 average residence time was 0.5 hour). To the polymer
solution was added a small amount of methanol to terminate
the polymerization reaction. Thereafter, the polymer
CA 02328828 2001-O1-08
142
solution was contacted with an aqueous solution containing
ml of concentrated hydrochloric acid in 1 liter of water
in a proportion of 1:1 with vigorous stirring by means of a
homomixer, thereby allowing the catalyst residue to
5 transfer into the aqueous phase. After allowing the
contacted mixture to stand, the aqueous phase was removed
by separation, and the polymer solution phase was washed
twice with distilled water to purify it and separated.
Subsequently, the polymer solution thus purified and
separated was then poured into acetone in an amount of 3
times as much as the polymer solution with vigorous
stirring. Then, the solid portion was collected by
filtration and thoroughly washed with acetone. Further,
the solid portion thus washed was introduced into acetone
so as to be 40 g/liter to extract TCD present in the
polymer at a temperature of 60 °C for 2 hours. After the
extraction, the solid portion was collected by filtration
and dried at 130 °C and 350 mmHg for 12 hours in a nitrogen
atmosphere.
2 ~ In the above-mentioned manner, a cycloolefin copolymer
composition comprising the ethylene/PhBH copolymer and the
ethylene/TCD copolymer was obtained in an amount of 53.4
g/hr, i.e., 26.7 g/liter. In the copolymer composition
thus produced, the component [Aa] was contained in an
2 5 amount of 25.8 ~ by weight. The MFR of the copolymer
composition, as measured at 260 °C under a load of 2.16 kg,
Was 2.9 g/10 min. The Tg of the component [Ba] was 142 °C.
CA 02328828 2001-O1-08
143
The results are shown in Table 5.
The procedure of Example 15 was repeated except for
varying the conditions to those shown in Table 5, to
prepare a cycloolefin copolymer composition comprising an
ethylene/PhBH copolymer and an ethylene/TCD copolymer.
The results are shown in Table 5.
Example 17
A 1-liter stainless steel autoclave was charged with
239 ml of toluene and 7.8 g of the ethylene/PhBH copolymer
(intrinsic viscosity [h]: 2.02 dl/g, Tg: -6.0 °C) obtained
by "Preparation of Cycloolefin Elastomer Component [Act]",
134 g of norbornene (NB) was fed at room temperature in a
nitrogen atmoshere, and the content in the autoclave was
stirred for 5 minutes. Subsequently, ethylene was passed
through the reaction system at ordinary pressure with
stirring to lay the system in an ethylene atmosphere.
2 0 Keeping the internal temperature of the autoclave at 70 °C,
ethylene was fed to the autoclave so that the internal
pressure was 4 kg/cmz. After stirring for 10 minutes, a
toluene solution containing ethylenebis(indenyl)zirconium
dichloride'~and methyl aluminoxan, which had been beforehand
2 5 prepared, was added to the system to initiate the
copolymerization reaction of ethylene and NB. At this
time, the concentration of ethylenebis(indenyl)zirconium
CA 02328828 2001-O1-08
144 '
dichloride in the system was 0.10 mmol/liter, and the
concentration of methyl aluminoxane in the system was 20
mmol/liter. During the polymerization, ethylene was
continuously fed to the system to keep the internal
pressure at 4 kg/cmz. After 20 minutes, isopropyl alcohol
was added to the system to terminate the polymerization
reaction. After release of the pressure, the polymer
solution was taken out of the autoclave, and contacted with
an aqueous solution of 5 ml of concentrated hydrochloric
acid in 1 liter of water in a proportion of 1:1 with
vigorous stirring by means of a homomixer, thereby allowing
the catalyst residue to transfer into the aqueous phase.
After allowing the contacted mixture to stand, the aqueous
phase was removed by separation, and the polymer solution
phase was washed twice with distilled water to purify it
and separated.
Then, the polymer solution thus purified and separated
was poured into acetone in an amount of 3 times as much as
the polymer solution with vigorous stirring to precipitate
2 0 a copolymer, and the solid portion (copolymer) was
collected by filtration and thoroughly washed with acetone.
Further, the solid portion was introduced into acetone so
as to be 40 g/liter and extracted the unreacted norbornene
(NB) present in the polymer at a temperature of 60 °C for 2
2 S hours. After the extraction, the solid portion was
collected by filtration and dried at 130 °C and 350 mmHg
for 12 hours in a nitrogen stream.
CA 02328828 2001-O1-08
145
In the above=mentioned manner, a cycloolefin copolymer
composition comprising the ethylene/PhBH copolymer and the
ethylene/NB copolymer was obtained. In the copolymer
composition thus produced, the component [Aa] was contained
S in an amount of 25.7 ~ by weight. The MFR of the copolymer
composition, as measured at 260 °C under a load of 2.16 kg,
was 2.6 g/10 min. The Tg of the component [Ba] was 135 °C.
The results are shown in Table 5.
Comparative Examples 6 - 8
The procedure.of Example 15 was repeated except for
varying the conditions to those shown in Table 5, to
prepare cycloolefin copolymer compositions.
The results are shown in Table 5.
As is apparent from the results of Comparative Example
7, when the intrinsic viscosity [~] of the elastomer
component [Aa] is lower than 0.5 dl/g, the impact strength
of the composition is reduced. Further, as is apparent
from the results of Comparative Example 8, when the glass
2 0 transition temperature (Tg) of the elastomer component [Aa]
is not lower than 15 °C, the impact strength of the
composition is reduced.
CA 02328828 2001-O1-08
146
Table 5
Elastomer Component
[Aa]
Example Kind of [~] Ph-NB Tg Refractive
Elastomer Content Index
(dl/g)(mold) (C) (nD)*2
Ex. 15 Ethylene~PhBH 1.91 12.2 2.4 1.5416
Ex. 16 Ethylene~PhBH 2.10 14.1 7.2 1.5457
Ex. 17 Ethylene~PhBH 2.02 5.0 -6.0 1.5302
omp. Ex. Component [Aa]
6 was not present
omp. Ex. Ethylene~PhBH 0.32 11.0 1.0 1.5391
7
omp. Ex. Ethylene~PhBH 1.87 17.0 20.6 1.5479
8
*2: measured at 25°C
CA 02328828 2001-O1-08
147
Table 5 (Continued)
Conditions
for Synthesis
of Component
[BOC]
.
in the presence
of Component
[ACC] *1
Example Kind of Content- Feed Rate Added Amount
Cycloolefinration of of
of (AOC]
Cycloolefin
Ethylene
(g/1) (1/hr) ( /1)
Ex. 15 TCD 60.0 30.6 6,g
Ex. 16 TCD 60.0 30.6 6,g
Ex. 17 NB 335.0 (pressure: 7.8
4 k /cm2
)
omp. Ex. TCD 60.0 30.6 0
6
'omp. Ex. TCD 60.0 30.6 6,g
7
omp. Ex. TCD 60.0 30.6 6,g
8
*1: Feed rate of nitrogen = 90.6 1/hr,
Feed rate of hydrogen = 0.85 1/hr.
In Example 17 and Comparative Example 6, neither nitrogen
nor hydrogen was fed.
CA 02328828 2001-O1-08
148
Table 5 (Continued)
Physical
Properties
of
Copolymer
Composition
Ex. ContentTg Refractive Refractive Izod Light ~R
of
of ~Ba~ Index of Index Impact Trans-
(Aa]
~ga~ Difference Strength mittance
between (g/10
(wtg) (C) (np)*2 (Aa] and (kg~cm/cm)(~) min)
(Ha]
Ex.lS 25.8 142 1.5436 0.0020 21 88 2.9
Ex.l6 26.0 141 1.5486 0.0029 10 88 2.7
Ex.l7 26.0 135 1.5291 0.0011 37 88 2.6
Comp. 0 149 1.5441 - 1 89 5.0
Ex.6
Comp. 25.9 143 1.5436 0.0045 2 85 2
8
Ex. .
7
Comp. 26.0 144 1.5436 0.0043 3 86 7
2
Ex. .
8
*2: measured at 25°C
