Method for producing cycloolefin polymers

Details Method for producing cycloolefin polymers Method for producing cycloolefin polymers

1999-07-29

2001-11-13

Wu, David W. (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S281000, C526S282000, C526S308000, C526S336000, C526S339000, C526S348600, C526S916000, C526S943000, C525S240000, C502S152000

Reexamination Certificate

active

06316560

ABSTRACT:

The invention relates to a process for preparing cycloolefin copolymers having high molar masses.
It is known from the literature that cycloolefin homopolymers and copolymers can be prepared using metallocene-aluminoxane catalyst systems (EP-A-283 164, EP-A-407 870). The polymerization of the cycloolefins proceeds here with retention of the rings and can be carried out in solvents or in bulk. As solvents, it is possible to use hydrocarbons.
EP 610 851 describes the preparation of cycloolefin polymers using suitable metallocene catalysts. EP 544 308 describes metallocene catalysts which are suitable for the polymerization of &agr;-olefins.
Cycloolefin copolymers can be prepared with a high cycloolefin content and then have a high glass transition temperature. This is associated with a high heat distortion resistance, which is why these polymers are suitable for use as thermoplastic molding compositions. Cycloolefin copolymers having a low cycloolefin content have a low glass transition temperature. At use temperature, they have a high ductility and can have elastomeric properties.
It is found that cycloolefin copolymers prepared by means of metallocene technology have a relatively low mass average molar mass. In addition, the use of ethylene as comonomer frequently results in formation of partially crystalline ethylene polymers as by-products which can significantly impair the transparency of the cycloolefin copolymers.
It is an object of the present invention to provide a process for preparing cycloolefin copolymers having a relatively high mass average molecular weight together with high transparency and excellent mechanical properties.
The object of the present invention has been achieved by a process for preparing a cycloolefin copolymer by polymerization of from 0.1 to 99.9% by weight, based on the total amount of monomers, of at least one polycyclic olefin, from 0 to 99.9% by weight, based on the total amount of monomers, of at least one monocyclic olefin and from 0.1 to 99.9% by weight, based on the total amount of monomers, of at least one acyclic 1-olefin in the presence of a catalyst system.
The polymerization is carried out in the liquid cycloolefin itself or in cycloolefin solution, with the pressure advantageously being above 1 bar.
The catalyst system used in the process of the invention comprises at least one metallocene of the formula I
where
M
1
is a metal of groups 3 to 10 or of the lanthanide series of the Periodic Table of the Elements,
R
1
are identical or different and are each a cyclopentadienyl group which may be substituted or an indenyl group which may be substituted and partially hydrogenated,
R
2
is a single- or multi-membered bridge which links the radicals R
1
and comprises at least one boron atom or at least one atom of group 14 of the Periodic Table of the Elements and may, if desired, comprise one or more sulfur or oxygen atoms and can, if desired, form a fused ring system together with R
1
,
R
3
is an anionic or nonionic ligand, where n=0, 1, 2, 3 or 4 depending on the valence of M.
The catalyst system to be used in the process of the invention can further comprise one or more cocatalysts.
The catalyst system to be used in the process of the invention is a highly active catalyst for olefin polymerization. Preference is given to using one metallocene and one cocatalyst. It is also possible to use mixtures of two or more metallocenes, particularly for preparing reactor blends or polyolefins having a broad or multimodal molar mass distribution.
The metallocene to be used in the process of the invention is preferably a compound of the formula I in which
M
1
is a metal of group 4 or the lanthanide series of the Periodic Table of the Elements,
R
1
are identical or different and are each a cyclopentadienyl group which may be substituted by one or more halogen atoms, one or more C
1
-C
40
-groups such as C
1
-C
10
-alkyl groups which may be halogenated, one or more C
6
-C
20
-aryl groups which may be halogenated, one or more C
6
-C
20
-aryloxy groups, one or more C
2
-C
12
-alkenyl groups, one or more C
7
-C
40
-arylalkyl groups, one or more C
7
-C
40
-alkylaryl groups, one or more C
8
-C
40
-arylalkenyl groups, SiR
4
3
, NR
4
2
, Si(OR
4
)
3
, Si(SR
4
)
3
or PR
4
2
, where R
4
are identical or different and are each a halogen atom, a C
1
-C
10
-alkyl group or a C
6
-C
10
-aryl group or form a ring system, or an indenyl group which may be substituted by one or more halogen atoms, one or more C
1
-C
40
-groups such as C
1
-C
10
-alkyl groups which may be halogenated, one or more C
6
-C
20
-aryl groups which may be halogenated, one or more C
6
-C
20
-aryloxy groups, one or more C
2
-C
12
-alkenyl groups, one or more C
7
-C
40
-arylalkyl groups, one or more C
7
-C
40
-alkylaryl groups, one or more C
8
-C
40
-arylalkenyl groups, SiR
4
3
, NR
4
2
, Si(OR
4
)
3
, Si(SR
4
)
3
or PR
4
2
, where R
4
are identical or different and are each a halogen atom, a C
1
-C
10
-alkyl group or a C
6
-C
10
-aryl group or form a ring system, where the indenyl group can also be partially hydrogenated and one of the structures R
1
must bear a substituent,
R
2
is a single- or multi-membered bridge which links the groups R
1
and is preferably
 ═BR
5
,═AIR
5
, -Ge-, -Sn-, -O-, -S-, ═SO, ═SO
2
, ═NR
5
, ═CO, ═PR or ═P(O)R
5
,
 where R
5
are identical or different and are each a hydrogen atom, a halogen atom, a C
1
-C
40
-group such as a C
1
-C
10
-alkyl group which may be halogenated, a C
6
-C
20
-aryl group which may be halogenated, a C
6
-C
20
-aryloxy group, a C
2
-C
12
-alkenyl group, a C
7
-C
40
-arylalkyl group, a C
7
-C
40
-alkylaryl group, a C
8
-C
40
-arylalkenyl group, SiR
6
3
, NR
6
2
, Si(OR
6
)
3
or PR
6
3
, where R
6
are identical or different and are each a halogen atom, a C
1
-C
10
-alkyl group or a C
6
-C
10
-aryl group or form a ring system, and
M
2
is silicon, germanium or tin,
R
3
are identical or different and are each a hydrogen atom, a C
1
-C
40
group such as a C
1
-C
10
-alkyl group, a C
1
-C
10
-alkoxy group, a C
6
-C
10
-aryl group, a C
6
-C
25
-aryloxy group, a C
2
-C
10
-alkenyl group, a C
7
-C
40
-arylalkyl group or a C
7
-C
40
-arylalkenyl group, an OH group, a halogen atom or NR
7
2
, where R
7
is a halogen atom, a C
1
-C
10
-alkyl group or a C
6
-C
10
-aryl group, or R
3
together with the atoms connecting them form a ring system, where n=1 or 2.
The metallocene to be used in the process of the invention is particularly preferably a compound of the formula II
where
M
1
is titanium, zirconium or hafnium,
R
1
is an indenyl group or a 4,5,6,7-tetrahydroindenyl group which is substituted in positions 2 and 3 exclusively by hydrogen atoms and in positions 4, 5, 6 and 7 may bear further substituents such as one or more halogen atoms and/or one or more C
1
-C
10
-groups in place of hydrogen,
R
1
is a cyclopentadienyl group which is substituted in position 3 by a C
2
-C
40
-group such as a C
2
-C
10
-alkyl group which may be halogenated, a C
6
-C
20
-aryl group which may be halogenated, a C
6
-C
20
-aryloxy group, a C
2
-C
12
-alkenyl group, a C
7
-C
40
-arylalkyl group, a C
7
-C
40
-alkylaryl group, a C
8
-C
40
-arylalkenyl group, SiR
4
3
, NR
4
2
, SIR(OR
4
)
3
, Si(SR
4
)
3
or PR
4
2
, where R
4
are identical or different and are each a halogen atom, a C
1
-C
10
-alkyl group or a C
6
-C
10
-aryl group or form a ring system, and in the further positions 2, 4 and 5 may bear further substituents such as one or more C
1
-C
10
-groups or one or more halogen atoms in place of hydrogen,
R
2
is a single-, two- or three-membered bridge which links R
1
and R
1′
in each case via position 1 and is preferably
 where R
5
are identical or different and are each a hydrogen atom, a C
1
-C
40
-group such as a C
1
-C
10
-alkyl group which may be halogenated, a C
6
-C
20
-aryl group which may be halogenated, a C
6
-C
20
-aryloxy group, a C
2
-C
12
-alkenyl group, a C
7
-C
40
-arylalkyl group, a C
7
-C
40
-alkylaryl group or a C
8
-C
40
-arylalkenyl group, where o&equ

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