Cyclopenta[I] phenanthrene-metal complex catalyst...

Details Cyclopenta[I] phenanthrene-metal complex catalyst... Cyclopenta[I] phenanthrene-metal complex catalyst...

1999-12-13

2001-09-04

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...

C526S097000, C526S131000, C526S943000, C526S127000, C502S152000, C556S011000, C556S007000

Reexamination Certificate

active

06284851

ABSTRACT:

BACKGROUND AND BRIEF SUMMARY OF THE INVENTION
The present invention relates to a process for preparing polymers based on monomers having a C═C double bond by homopolymerization or copolymerization of these monomers in the presence of a catalyst system comprising a metallocene complex A) and a compound B) capable of forming metallocenium ions and, if desired, an organometallic compound of main group I, II or III of the Periodic Table of the Elements C), catalyst systems which are suitable for polymerizing monomers having a C═C double bond and comprise as active constituents
A) a metallocene complex of the formula (I)
where the substituents and indices have the following meanings:
R
1
to R
11
are hydrogen, C
1
-C
10
-alkyl, 5- to 7-membered cycloalkyl which may in turn bear C
1
-C
6
-alkyl groups as substituents, C
6
-C
15
-aryl or arylalkyl, where two adjacent radicals R
1
to R
8
may together form a cyclic group having from 4 to 15 carbon atoms, or Si(R
12
)
3
,
where R
12
is C
1
-C
10
-alkyl, C
6
-C
15
-aryl or C
3
-C
10
-cycloalkyl,
M is a metal of transition groups III to VI of the 40 Periodic Table of the Elements or a metal of the lanthanide series,
X are identical or different and are hydrogen, halogen, C
1
-C
10
-alkyl, C
6
-C
15
-aryl, C
1
-C
10
-alkoxy or C
6
-C
15
-aryloxy
and
n is 1, 2, 3, 4 or 5, where n corresponds to the valence of M minus 1,
B) a compound capable of forming metallocenium ions and, if desired, C) an organometallic compound of main group I, II or III of the Periodic Table of the Elements, metallocene complexes of the formula (I)
where the substituents and indices have the following meanings:
R
1
to R
11
are hydrogen, C
1
-C
10
-alkyl, 5- to 7-membered cycloalkyl which may in turn bear C
1
-C
6
-alkyl groups as substituents, C
6
-C
15
-aryl or arylalkyl, where two adjacent radicals R
1
to R
8
may together form a cyclic group having from 4 to 15 carbon atoms, or Si(R
12
)
3
,
where R
12
is C
1
-C
10
-alkyl, C
6
-C
15
-aryl or C
3
-C
10
-cycloalkyl,
M is a metal of transition groups III to VI of the Periodic Table of the Elements or a metal of the lanthanide series,
X are identical or different and are hydrogen, halogen, C
1
-C
10
-alkyl, C
6
-C
15
-aryl, C
1
-C
10
-alkoxy or C
6
-C
15
-aryloxy
and
n is 1, 2, 3, 4 or 5, where n corresponds to the valence of M minus 1.
The present invention further relates to polymers which are based on monomers having a C═C double bond and are obtainable by homopolymerization or copolymerization of these monomers in the presence of a catalyst system comprising a metallocene complex A) and a compound B) capable of forming metallocenium ions and, if desired, an organometallic compound of main group I, II or III of the Periodic Table of the Elements C), and also fibers, films and moldings comprising these polymers and the use of metallocene complexes (I) as components in catalyst systems or as catalysts.
Syndiotactic polymers of styrene are known. Owing to their property profile, eg. high hardness, high stiffness, dimensional stability and low dielectric constants, they can be used, for example, as electrical or mechanical components.
DETAILED DESCRIPTION OF THE INVENTION
It is an object of the present invention to find novel catalyst systems which can be used at relatively high polymerization temperatures, preferably above 60° C., have a high polymerization activity and give a polymer having a high proportion, preferably above 80% (determined by extraction of the crude polymer with n-butanone) of syndiotactic structural units and a high molecular weight M
w
.
We have found that this object is achieved by a process for preparing polymers based on monomers having a C═C double bond by homopolymerization or copolymerization of these monomers in the presence of a catalyst system comprising a metallocene complex A) and a compound B) capable of forming metallocenium ions and, if desired, an organometallic compound of main group I, II or III of the Periodic Table of the Elements C), wherein the metallocene complex A) used is a compound of the formula (I)
where the substituents and indices have the following meanings:
R
1
to R
11
are hydrogen, C
1
-C
10
-alkyl, 5- to 7-membered cycloalkyl which may in turn bear C
1
-C
6
-alkyl groups as substituents, C
6
-C
15
-aryl or arylalkyl, where two adjacent radicals R
1
to R
8
may together form a cyclic group having from 4 to 15 carbon atoms, or Si(R
12
)
3
,
where R
12
is C
1
-C
10
-alkyl, C
6
-C
15
-aryl or C
3
-C
10
-cycloalkyl,
M is a metal of transition groups III to VI of the Periodic Table of the Elements or a metal of the lanthanide series
X are identical or different and are hydrogen, halogen, C
1
-C
10
-alkyl, C
6
-C
15
-aryl, C
1
-C
10
-alkoxy or C
6
-C
15
-aryloxy
and
n is 1, 2, 3, 4 or 5, where n corresponds to the valence of M minus 1,
by catalyst systems which are suitable for polymerizing monomers having a C═C double bond and comprise as active constituents
A) a metallocene complex of the formula (I)
B) a compound capable of forming metallocenium ions and, if desired,
C) an organometallic compound of main group I, II or III of the Periodic Table of the Elements, by metallocene complexes of the formula (I)
where the substituents and indices have the following meanings:
R
1
to R
11
are hydrogen, C
1
-C
10
-alkyl, 5- to 7-membered cycloalkyl which may in turn bear C
1
-C
6
-alkyl groups as substituents, C
6
-C
15
-aryl or arylalkyl, where two adjacent radicals R
1
to R
8
may together form a cyclic group having from 4 to 15 carbon atoms, or Si(R
2
)
3
,
where R
12
is C
1
-C
10
-alkyl, C
6
-C
15
-aryl or C
3
-C
10
-cycloalkyl,
M is a metal of transition groups III to VI of the Periodic Table of the Elements or a metal of the lanthanide series,
X are identical or different and are hydrogen, halogen, C
1
-C
10
-alkyl, C
6
-C
15
-aryl, C
1
-C
10
-alkoxy or C
6
-C
15
-aryloxy
and
n is 1, 2, 3, 4 or 5, where n corresponds to the valence of M minus 1,
by polymers which are based on monomers having a C═C double bond and are obtainable by homopolymerization or copolymerization of these monomers in the presence of a catalyst system comprising a metallocene complex A), a compound B) capable of forming metallocenium ions and, if desired, an organometallic compound of main group I, II or III of the Periodic Table of the Elements C), wherein the metallocene complex A) used is a compound of the formula (I)
where the substituents and indices have the following meanings:
R
1
to R
11
are hydrogen, C
1
-C
10
-alkyl, 5- to 7-membered cycloalkyl which may in turn bear C
1
-C
6
-alkyl groups as substituents, C
6
-C
15
-aryl or arylalkyl, where two adjacent radicals R
1
to R
8
may together form a cyclic group having from 4 to 15 carbon atoms, or Si(R
12
)
3
,
where R
12
is C
1
-C
10
-alkyl, C
6
-C
15
-aryl or C
3
-C
10
-cycloalkyl,
M is a metal of transition groups III to VI of the Periodic Table of the Elements or a metal of the lanthanide series,
X are identical or different and are hydrogen, halogen, C
1
-C
10
-alkyl, C
6
-C
15
-aryl, C
1
-C
10
-alkoxy or C
6
-C
15
-aryloxy
and
n is 1, 2, 3, 4 or 5, where n corresponds to the valence of M minus 1,
by fibers, films and moldings comprising the polymers of the present invention and also by the use of the metallocene complexes (I) of the present invention as components in catalyst systems or as catalysts.
Suitable monomers are generally all those which have a polymerizable carbon-carbon (C═C) double bond. Examples are linear alkenes having from 2 to 20 carbon atoms, where the double bond may be in an internal or terminal position, and cyclic or bicyclic alkenes having from 3 to 20 carbon atoms, where the C═C double bond can be in an endo or exo position. The linear and cyclic alkenes can be substituted by functional groups such as halogen, an ester group, a —COOH group or a nitrile group. Examples of such monomers are vinyl chloride, ethyl acrylate, methyl acrylate, methyl methacrylate and acrylonitrile. The linear and cyclic alkenes are preferably hydrocarbons without heteroato

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