Method for producing a cycloolefin copolymer

Details Method for producing a cycloolefin copolymer Method for producing a cycloolefin copolymer

1999-07-29

2002-04-02

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...

C526S160000, C526S161000, C526S943000, C526S280000, C526S281000, C502S152000, C502S155000

Reexamination Certificate

active

06365686

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.
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 molar mass together with high transparency.
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 to be used in the process of the invention comprises at least one metal complex comprising a metal of groups 3 to 10 or of the lanthanide series of the Periodic Table of the Elements and a conjugated &pgr; system coordinated to the metal. The conjugated z system coordinated to the metal may be substituted by a group which is likewise coordinated to the metal atom and results in the strained geometry of the metal complex. Comparable structures are described in EP-A-416 815, in EP-A-418 044 and in EP-A-698 618.
The metal complex to be used in the process of the invention is preferably a compound 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
is a delocalized acyclic &pgr; system such as C
4
-C
20
-alkenyl, C
4
-C
20
-alkynyl, C
3
-C
20
-allyl, C
4
-C
20
-alkadienyl, C
4
-C
20
-polyenyl or a comparable structure which may comprise up to 5 hetero atoms, or an unsubstituted or substituted delocalized C
5
-C
40
-cyclic &pgr; system or a comparable structure which may comprise up to 5 hetero atoms,
R
2
is a single- or multi-membered bridge which links the radicals R
1
and R
3
and comprises at least one atom of group 14 of the Periodic Table of the Elements or at least one boron atom and may comprise one or more sulfur or oxygen atoms and can form a fused ring system together with R
1
,
R
3
is an anionic or nonionic ligand which is coordinated to M
1
and comprises one or more nitrogen, phosphorus, oxygen and/or sulfur atoms and can form a fused ring system together with R
2
, and
R
4
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 metal complex and one cocatalyst. It is also possible to use mixtures of two or more metal complexes, particularly for preparing reactor blends or polyolefins having a broad or multimodal molar mass distribution.
Preference is given to a metal complex comprising a metal of group 4 or the lanthanide series of the Periodic Table of the Elements. Preference is also given to a metal complex which comprises a delocalized cyclic &eegr;
5
-coordinated &pgr; system. Preference is given to delocalized cyclic &pgr; systems such as cyclopentadienyl, indenyl, fluorenyl or substituted cyclopentadienyl, substituted indenyl or substituted fluorenyl or comparable structures which may comprise up to 5 hetero atoms. Here, one or more of the atoms of the delocalized cyclic &pgr; system may be substituted, in which case the substituents may be identical or different and may comprise, in addition to hydrogen, atoms of group 14 of the Periodic Table of the Elements and/or one or more hetero atoms such as those of groups 15, 16 and 17 of the Periodic Table of the Elements. Two or more of the substituents can form a ring. Examples of substituted delocalized cyclic &pgr; systems are methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, t-butylcyclopentadienyl, dimethylcyclopentadienyi, diethylcyclopentadienyl, diisopropylcyclopentadienyl, di-t-butylcyclopentadienyl and tetramethylcyclopentadienyl.
The metal complex to be used in the process of the invention is particularly preferably a compound of the formula (la)
in which
M
1
is a metal of group 4 or the lanthanide series of the Periodic Table of the Elements,
R
2
is a single- or multi-membered bridge which links the &eegr;
5
-coordinated cyclic &pgr; system and R and is preferably
 ═BR
6
, ═AIR, —Ge—, —Sn—, —O—, —S—, ═SO, ═SO
2
, ═NR, ═CO, ═PR
6
or ═P(O)R
6
,
where R
6
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
7
3
, —NR
7
2
, —Si(OR
7
)
3
, —Si(SR
7
)
3
or —PR
2
,
where R
7
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 o≧1, and
M
2
is silicon, germanium or tin,
R
3
is O, S, NR
8
, PR
8
or an uncharged 2-electron donor ligand selected from the group consisting of OR
8
, SR
8
, NR
8
2
, PR
8
2
, where R
8
is a hydrogen atom, a halogen atom, a C
1
-C
40
-group such as a C
1
-C
8
-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
9
3
, —NR
9
2
, —Si(OR
9
)
3
, —Si(SR
9
)
3
or —PR
9
2
, where R
9
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,
R
4
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
2
5-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
10
2
, where R
10
is a halogen atom, a C
1
-C
10
-alkyl group or a C
6
-C
10
-aryl group, or R
4
together with the atoms connecting them form a ring system, where n=1 or 2,
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 or a C
8
-C
40
-arylalkenyl group, —SiR
11
3
, —NR
11
2
, —Si(OR
11
)
3
, —Si(SR
11
)
3
or —PR
11
2
, where R
11
are identical or different and are

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