(CO)POLYMERES A BASE DE METALLOCENES; METHODE DE PREPARATION ET UTILISATION COMME CATALYSEURS

METALLOCENE (CO)POLYMERS, PROCESS FOR THEIR PREPARATION AND THEIR USE AS CATALYSTS

Abrégé anglais

HOE 91/F 007
Abstract
Metallocene(co)polymers, process for their preparation
and their use as catalysts.
An immobile (heterogeneous) metallocene ratalyst com-
ponent which can advantageously be used for olefin
polymerization is obtained by homopolymerization of
appropriately substituted (vinyl group-containing) metal-
locenes of group IVb of the periodic table or by
copolymerization of such metallocenes with (di)vinyl-
aromatic compounds.

Revendications

- 22 - HOE 91/F 007
THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of an immobile metal-
locene catalyst component, wherein a metallocene of
formula I
<IMG> (I)
and/or of formula II
<IMG> (II),
in which
M1 is zirconium or hafnium and
CP is a cyclopentadienyl radical,
R1 and R2 are identical or different and are a
hydrogen atom, a halogen atom, a C1-C10-alkyl
group, a C1-C10-alkoxy group, a C7-C20 arylalkyl
group, a C5-C10-aryl group or a C5-C10-aryloxy
group, and
R1 and R2 Can a180 be 1inked tO One anOthar and
together with M1 can form a metallo ring,
the radicals R3 are identical or different and are a
hydrogen atom, a halogen atom, a C1-C10-alkyl
group, a C6-C10-aryl group, a C7-C20-arylalkyl
group, a C1-C10-fluoroalkyl group or an organo-
metallic radical, such as C1-C10-trialkylsilyl,
C6-C10-aryl-C1-C10-dialkylsilyl, C1-C10-alkyl-C6-C10-
diarylsilyl or C6-C10-triarylsilyl,
R4 and R5 are identical or different and are a vinyl
group, a C6-C18-arylvinyl group, a C1-C8alkylvinyl

- 23 -
group or a C8-C18-vinylaryl group, all of which
may be substituted,
R6 and R7 are identical or different and are a cyclo-
pentadienyl, indenyl or fluorenyl radical, it
being possible for said rings together with M1 to
form a sandwich structure,
R8 and R9 are identical or different,
are substituents of R8 and R7 and have the mean-
ings given for R3, R4 and R5, with the proviso
that R6 and R7 can be monosubstituted or poly-
substituted by R8 or R9, but at least one ring R6
or R7 must carry at least one radical R8 or R9
having the meaning of R4 and R5, and
R10 has the meaning shown in formulae III-VII
<IMG>
(III) (IV) (V) (VI) (VII),
where
M2 is silicon, germanium or tin and
R11, R12, R13 and R14 are identical or different and
are a hydrogen atom, a halogen atom, a
C1-C10-alkyl group, a C1-C10-fluoroalkyl group, a
C6-C10-aryl group, a C6-C10-fluoroaryl group, a
C1-C10-alkoxy group, a C6-C10-aryloxy group or a
C7 C20-arylalkyl group,
R11 and R12, R13 and R14, R11 and R13 or R12 and R14
together with the atoms linking them can form a
ring system and
m and n are identical or different and are a
number from 0 to 5, where m+n must be ? 1,
is homopolymerized or copolymerized, or a com-
pound of formula I and/or of formula II is
copolymerized with a (di)vinyl-aromatic compound.

- 24 -
2. The process as claimed in claim 1, wherein, in
formulae I and II,
R1 and R2 are identical or different and are a
hydrogen atom, a halogen atom, a C1-C4-alkyl
group, a C1-C4-alkoxy group, a C7-Cl4-arylalkyl
group, a C6-C10-aryl group or a C6-C10-aryloxy
group, and
R1 and R2 can also be linked to one another and
together with M1 can form a metallo ring,
the radicals R3 are identical or different and are a
hydrogen atom, a halogen atom, a C1-C4-alkyl
group, a C6-C10-aryl group, a C7-C14-arylalkyl
group, a C1-C6-fluoroalkyl group or an organo-
metallic radical, such as C1-C10-trialkylsilyl,
C6-C10-aryl-C1-C6-dialkylsilyl, C1-C4-alkyl-
C6-C10-diarylsilyl or C6-C10-triarylsilyl,
R4 and R5 are identical or different, preferably
identical, and are a vinyl group, a C6-C18-aryl-
vinyl group, a C1-C8-alkylvinyl group or a
C6-C18-vinylaryl group, which groups may be
substituted by a C1-C4-alkoxy group, C1-C4-alkyl
group or OH group,
R6 and R7 are identical or different and are a cyclo-
pentadienyl, indenyl or fluorenyl radical, it
being possible for said rings together with M1 to
form a sandwich structure,
R8 and R9 are identical or different,
are substituents of R6 and R7 and have the mean-
ings given for R3, R4 and R5, with the proviso
that R6 and R7 can be monosubstituted or poly-
substituted by R8 or R9, but at least one ring R6
or R7 must carry at least one radical R8 or R9
having the meaning of R4 and R5, and

- 25 -
R10 has the meaning shown in formulae III-VII, where
M2 is silicon or germanium and R11, R22, R13 and R14
are identical or different and are a hydrogen
atom, a halogen atom, a C2-C6-alkyl group, a C2-
C6-fluoroalkyl group, a C6-C10-aryl group, a C6-
C10-fluoroaryl group, a C1-C8-alkoxy group, a C6-
C10-aryloxy group or a C7-C14-arylalkyl group,
R11 and R12, R13 and R14, R11 and R13 or R12 and R14
together with the atoms linking them can form a
ring system, and
m and n are identical or diffPrent and are a
number from 0 to 5, where m+n must be ? 1.
3. The process as claimed in claim 1 or 2, wherein, in
formulae I and II,
R1 and R2 are identical or different and are a
hydrogen atom, a halogen atom, a C1-C4-alkyl group
or a C6-C10-aryl group, and
R1 and R2 can also be linked to one another and
together with M1 can form a metallo ring,
the radicals R3 are identical or different and are a
hydrogen atom, a halogen atom, a C1-C4-alkyl
groupl a C6-C10-aryl group or an organometallic
radical, such as C1-C10-trialkylsilyl,
R6 and R7 are a cyclopentadienyl radical, and
R10 has the meaning shown in formulae III-V, where
M2 is sillcon and R11, R12, R13 and R14 are identical
or different and are a hydrogen atom, a halogen
atom, a C1-C6-alkyl group or a C6-C10-aryl group,
and
R11 and R12, R13 and R14, R11 and R13 or R12 and R14
together with the atoms linking them can form a
ring system.
4. The process as claimed in one or more of claims 1-3,

- 26 -
wherein the polymerization is initiated by the
action of heat or by means of a free radical forming
agent.
5. The process as claimed in one or more of claims 1-
4, wherein the polymerization is initiated by means
of a free radical forming agent.
6. The process as claimed in claim 5, wherein the free
radical forming agent is .alpha.,.alpha.'-azo-isobutyronitrile.
7. An immobile metallocene catalyst component, which
can be prepared by the process as claimed in one or
more of claims 1-6.
8. The use of an immobile metallocene catalyst com-
ponent as claimed in claim 7 as catalyst in olefin
polymerization.

Description

HOECHS~ AKTIENGESELLSCHAF~ ~OE 91/F 007 ~r,LO/~e
De~cription 2~ 23 ~ ~ ?J 9
Metallocene (co)polymers, proce~ for their prepara~ion
and their use as catalysts.
The present invention primarily relates to a proce~s for
the preparation of an immobile (heterogeneou5) metal-
locsne cataly6t component by homopolymerization of
metallocenes con~aining vinyl functional group~ or by
copolymerization of such mekallocenes with (di)vinyl-
aromatic compounds. The polymers prepared in this way
have advantageous properties as catalysts in olefin
polymerization.
Metallocenes of transition metals are known as catalyst
components (cf. US 4 522 982, US 4 542 199 and
EP-A 128045). Together with aluminoxanes they form
homogeneous transition metal catalysts which are soluble
in aromatic and aliphatic hydrocarbons. These catalysts
are highly active. Together with ~alts of non-coordina~-
ing anions, metallocenes also form an active system for
olefin polymerization (cf. EP-A 277 003~4).
However, soluble catalysts have disadvantages if they are
to be us0d in existing indu~trial plant~, ~ince the
latter are as a rule equipped ~or the use of hetero-
geneous cataly~t system~.
Metallocene catalyst6 in which a zirconocene or titano
cene component and an aluminoxane are applied conjointly
from a solution to a silicate ~upport have also been dis-
closed (cf. EP-A 206 794). However, this catalyst system
has low activity. Moreover, the catalyst components are
not anchored sufficiently firmly to the ~upport and can
30 thus be extracted during the polymerization.
It is also known that metallocene compounds containing
silyl ether radicals can be applied to silicate support~
with the formation of siloxane bridges (cf~EP-A 293 81S~.

- 2 ~ 2~
For this purpose it i~ necessary to remove the water
bonded by adsorption to the support material by drying
for several hours at a temperature of at most 800C.
It is also known that a heterogeneous metallocene
catalyst is obtained if a metallocene compound containing
olefin groups is reacted with a poly(methylhydrogeno-
siloxane) under hydrosilylation catalysis
(cf. DE-05 ~German Offenlegungs~chrift~ 33 40 772~.
These polymerization catalysts are distinguished by only
moderate polymerization activity, especially in compari-
son with their soluble precur~ors.
In Pure and Appl. Chem., Vol. 58 (1986) 617-622 the
copolymerization of (Cp-vinyl) CpTiC12 (Cp = cyclo-
pentadienyl) and the like with vinylbenzene i8 described.
~here is no indication of a possible use of the reaction
product as a catalyst. ExperLments have shown that
titanocene-based copolymers of khi~ type have only a low
polymerization activity.
The object was, there~ore, to find a catalyst syst~m
which is insoluble in con~entional solvents - including
aromatic solvents - but nevertheless has a high polymeri-
zation activity.
It has been found that the abovementioned disadvantage~
can be overcome if a æirconocene or hafnocene containing
vinyl functional groups is polymerized, optionally
together with a ~di~vinyl-aromatic compound, and the
resulting polymer is used as pol~merization catalyst.
The present invention therefore relates to a process for
the preparation of an immobile metallocene catalyst
component, wherein a me~allocene of formula I
.

-- 3 ~
2 ~ ~ 9 ~ 2 9
R1 ~ lCpP~ ~m~ m] ( I )
M1
R2/ ~ ~ [CpR 5 "R n]
and/or of formula II
l8
" \ ~II),
R7' R2
in which ~5
Ml is zirconium or hafnium and
Cp is a cyclopentadienyl radical,
Rl and R2 are identical or different and are a hydrogen
atom, a halogen atom, a Cl-C~ lkyl group, a
Cl-C1O-alkoxy groupO a C7-C2D-arylalkyl group,
C6-C1O-aryl group or a C6-C1O-aryloxy group, and
Rl and R~ can also be linked to one another and
together with Ml can form a metallo ring,
the radicals R3 are identical or di~ferent and are a
hydrogen atom, a halogen atom, a Cl-C1O-al~yl group,
a C8 C1O-aryl group, a C7-C20~arylalkyl group, a Cl-C10-
fluoroalkyl group or an organometallic radical, such
as cl-C10-trialkyl~llyl/ CB_C10~arY1_C1 C10_dia1kY1_
~ilyl 7 Cl-C1O-alkyl-C6-C1O-dia~ylsilyl or CB_C10-
triarylsilyl,
R4 and R5 are identical or different and are a vinyl
group, a C6-Cl8-arylvinyl group, a Cl-C8-alkylvinyl
group or a C6-Cl~-~inylaryl group, all o~ which may
be ~ubstituted,
R6 and R7 are identical or dif~erent and are a cyclo-
pentadienyl, indenyl or fluorenyl radical, it being
possible for said rings together with Ml to form a

- 4 ~ ~ 2 ? 3
sandwich struc~ure,
R8 and R9 are identical or different,
are sub~tituent6 of R6 and R7 and have the meanings
given for R3, R" and Rs, with the proviso that R6 and
R7 can be monosubstituted or polysubstituted by R8 or
R9, but a~ least one ring R~ or R7 must carry at
least one radical R8 or R9 having the meaning of R~
and R5, and
Rl has the meaning ~hown in formulae III-VII
R11 R~1 ~" R~3 R~ R~3 R11 713
-C- M2 -C~C- -C--M2- M2_M2
10l 12 1 2 l 12 R14 l 12 R1~ R12 R14
where
MZ is silicon, germanium or tin and
Rll, Rl2, R13 and R14 are identical or different and
are a hydrogen atom, a halogen atom, a Cl-C1O-alkyl
group, a Cl-C1O-fluoroalkyl group, a C6 C1O-aryl group,
a C~-C1O-fluoroaryl group, a C1-C10-alkoxy group, a
C6-C1O-aryloxy group or a C7~C20-~rylalkyl group,
R and R1Z, R13 and R14, R11 and R13 or R12 d R14
together with the atoms linking them can form a xing
system and
m and n ~re identical or different and are a number
from O to 5, where m~n muRt be ~ 1,
is homopol~merized or copolymerized, or a compound
of formula I and/or of fo~mula II is copolymerized
with a (di)vinyl-aromatic compound.
The Lmmobile metallocene catalyst components prepared by
the process according to the invention are novel and are
likewise a subject of this invention.
Metallocene catalyst component accoxding to the invention
thus signifies:
a) homopolymers of compounds I and II,

~ 5 ~ 2~
b) copolymer~ o~ one or more compounds I and one or
more compounds II,
c) copolymers o~ one or more compounds I and one or
more (di)vinyl-aromatic compound~,
d) copolymers of one or more compounds II and one or
more (di)vinyl-aromatic compounds, and
e) copolymers of one or more compounds I and II and one
or more (di)vinyl-aromatic compounds.
Preferably, in formulae I and II
Rl and R2 are identical or different and are a hydrogen
atom, a halogen atom, a C1-C4-alkyl group,
Cl-C4-alkoxy group, a C7-Cl4-arylalkyl group, a
C6-Cl~-aryl group or a C6-C1O-aryloxy group, and
R1 and R2 can also be linked to one another and
together with M1 can form a metallo ring,
the radicals R3 are identical or different and are a
hydrogen atom, a halogen atom, a Cl-C4-alkyl group,
a C6-C1O-aryl group, a C7~Cl4-arylalk~Tl group, a
Cl-C6-fluoroalkyl group or an organometallic radical,
such as C1-C10-trialkylsilyl, C~--ClD--ar~Tl--Cl--CB--di--
alkylsilyl, Cl-C4-alkyl-CG-C10-diarylsilyl or
C6-ClO-triarylsilyl,
R4 and Rs are identical or differen~, pre~exably identi-
cal~ and are a vlnyl group, a C~-Cl~-aryl~Tinyl group,
a Cl-C8-alkylvinyl group or a C6-C18-vinylaxyl group,
which group~ may be substituted by a Cl-C4-alkoxy
group, Cl-C4-alkyl group or OH group,
R6 and R' are identical or different and are a cyclo-
pentadienyl, indenyl or fluorenyl radical, it being
possible for said rings together with M1 to form a
sandwich structure,
R8 and R9 are identical or different,
are substituents of R6 and R7 and have the meanings

6 - ?J~ 3 ~
given for R3, R4 and R5~ with the provi~o t~at R6 and
R7 can be mono6ub~tituted or polysubstituted by RD or
R9, but at lea~t one ring R6 or R7 mus~ carry a~
least ~ne radical R8 or R~ having the meaning of R4
and R5l and
Rl has the meaning shown in formulae III-YII, where
M2 is silicon or germanium and Rll, Rl2, Rl3 and R are
identical or differen~ and are a hydrogen a~om, a
halogen a~om, a C1-C6-alkyl group, a C1~C6-fluor~alkyl
group, a C6-C10-aryl group, a C6-C10-fluoroaryl group/
a Cl-C6-alkoxy group~ a C6-C10-a~yloxy group or a
C~-C14-arylalkyl ~roup,
R1l and R12 R13 and R14, R11 and Rl3 o~ R and R
together with the atoms linking them can form a ring
system, and
m and n are identical or different and are a number
from O to 51 where m+n mu~t be 2 l.
In particular,
R1 and R2 are identical or different and are a hydrogen
atom, a halogen atom, a C1-C4-alkyl group or a
C6-C1O-aryl group, and
R1 and R2 can al~o be linked to one another and
tog2ther with M1 can form a metallo ring,
the radical~ R3 are identical or dif~erent and are a
hydrogen atom, a halogen atom, a C1-C4-alkyl yroup,
a C~-C1O~aryl group or an organometallic radical,
~uch a~ C1-C10-trialkylsilyl,
R6 and R7 are a cyclopentadienyl radical, and
Rl has the meaning shown in formulae III-V, where
M2 is ~ilicon and R11, R12~ R13 and R14 are identical or
different and are a hydrvgen atom, a halogen atom,
a Cl-C6-alkyl group or a C6-C10-aryl group, and
11 d Rl2 ~13 and R14, Rl1 and ~13 or R and R
together with the atoms linkin~ them can form a ring
.
,

~ 7 ~ 2~
system.
Rl is pre~erably a dialkylsilyl group or a 1,2-alkanediyl
group, in particular a dimethylsilyl group or 1,2-ethane~
diyl group.
R1l and R12 or R13 and R14 can be linked to one anothor with
the formation of ~pirocyclic ~ystems such as
Q ~
in the ~ame way as Rl~ and Rl3 or Rl2 and R14 can form the
following ring system X
O O
1 1
f C\
R12 Rl4
Examples of suitable metallocenes of formula I are:
cl~zr ~] L~I (1~
[~] ~ ] ~1-2)
Cl2Zr ~ [~
~ (1~4)
rl
~ ~ ~2

~ - 8 ~ 2 9
_ ~ ~ 2
Example~ for for~la II are:
~ ,
CIzZr~ (~
/~ '
CI~Zr ~ Si ~ (11-2)
~/
~~
CI~Zr Si ~ (11-3).
(Sub~tituent "\" i8 a methyl group).
The preparation processes for the metallocenes described
are known ln principle; cf. Journal of Organometallic
Chem. 288 (lg85) 63-67, EP-A 320 762 and the illustrative
embodiments.
Examples of (di)vinyl-aromatic compounds to be u~ed
according ~o the i~vention for copolymerization ares
4-vinylanisole, 9-vinylanthracene, 4-ethoxystyrsne,
vinylmesitylene, 2-, 3- or 4 vi~yltoluene, 8tyr2ne,
4 vinylbiphenyl, 4-vinylveratrole, 2-vinylnaphthalene and
divinylbenzene, in particular styrene (vinylben ene), or
mixtures thereof. Divinylbenzene is preferably employed
,' "'. ' .
. - ,

9 2 ~ S .~
if cro~slinking i8 desired during ~he pol~merization.
- These sub~tances are commercially available.
If the metallocene compounds I and/or II are pol~meriz~d
with vinylbenzene and divinylbenzene, they contain at
least one vinyl yroup. If the compounds I and/or II are
copolymerized with vinylbenzene but without divinyl-
benzene, they must then have at lea~ 2 vinyl group~.
~he (co)polymerization can take place either by the
action of heat (without free radical initiator) or
tpreferably) by free radical catalysis. In the latter
case, free radical forming agent~ are added in catalyti-
cally effective amounts to the reaction mixture. The
suitability of a substance as a catalyst (free radical
fonming agent) for the proce~ according to the invention
results in particular from it~ half life at a given
temperature. ~ Azo-isobutyronitrile is pref~rabl~
used. However, numerous compounds from the ~ubstance
category comprising organic peroxides are also ~uitable
for the said purpose.
~xampleæ of ~uch compounds are: tert-butyl perbenzoa~e,
2,2-bis-(butylperoxy)butane, di-tert-butyl dipex-
phthalate, tert-butyl perisononan~te, tert-butyl per-
acetate, 2,5-dlmethylhexane 2,5-diperbenzoate, 3,5,5-
trimethylcyclohexanone perk~tal, mono-text-butyl per-
maleate, tert-butyl perisobutyrate, p-chlorobenzoyl
peroxide, tert-butyl peroctoate; benzoyl peroxide,
diacetyl peroxide, succinyl peroxidel propionyl peroxide,
capryloyl peroxide, lauroyl peroxide, decanoyl peroxide,
isononanoyl peroxide, tert-butyl perpivalate or 2,4-di-
chlorobenzoyl peroxide.
For polymerization, the reactants are introduced into ahydrocarbon, preferably into an aromatic hydrocarbon, in
particular toluene or xylene, and heated for 1 to 24 h,
preferably 4 to 10 h, at 60-140C, pref~rably 80-90C,
and 0.1 g portions of ~,~'-azo-isobutyronitrile are added

l o - 2 ~ 2 ~
1 to 4 times during the reaction. The ~upernatant i~
decanted off from khe resul~ing polymer, which i5 ~wollen
in aromatic solvents, and the product i~ wa~hed with the
solvent used and then dried under vacuum. The residue i8
5 washed several tLmes with saturated hydrocarbon, prefer-
ably n-hexane or n-pentane, and dried under vacu~m.
The vinylmetallocenes of foxmulaP I or II C8n al~o
readily be homopolymerized by the action of heat (without
a free radical initiator~. This can be carried out in a
high-boiling inert solvent, such as n-octane or xylene,
or also, preferably, withou~ a solven~. With ~his pro-
cedure a solid is formed which is insoluble in hydro-
carbons.
~he homopolymers or copolymers according to the invention
can advantageously be u ed as catalysts for the poly-
merization of 1-olefins of the formula
Rl5 - CH = CH2,
in which R15 iB hydrogen or a straight-chain or branched
alkyl group, preferably ethylene, propylene or 4-methyl-
pent(1)-ene~
In addition, the catalyst can al~o be used ~or the
pol~merization o~ cyclic olefins, such as cyclopentene,
cyclohexene or norbornene, diolefins and cyclic
diolefins.
It i~ also possible to copol~merize several olefins of
the abovementioned formula or cycloolefin~ with one
another.
For the preparation of polyolefins, a catalyst system is
preferably used which, in addition to the metallocene
polymer according to the invention, comprises an alumin-
oxane as cocatalyst. The preparation and the use of ~uch
aluminoxanes are known (S. Pasynkiewicz, Polyhedron 9
.' ' ' '

- 11 ?J~ 7(~'~
(1990) 42g and EP-A 302 424).
It is also possible ~o use a salt-like compound o~ the
formula RXNH4jsBR~4 or of the formula R3PHBR~4 as co-
catalyst instead of (or in addition to) an aluminoxane.
5 In these formulae x is 1, 2 or 3, R is al~yl or aryl,
which may be identical or different, and R' is aryl,
which may also be fluorinated or partially fluorinated.
In this case, ~he cat~lyst consists of the reaction
product of ~he me~.allocene polymer with one of the said
compounds (cf. ~P-A 277 004).
Furthermore, the metallocene polymer described above can
also be reacted with an alkylating agent, such as a
Grignard or lithium compound, in particular Li alumino-
alkyl and especially methyllithi~m. This reaction is of
course not required in the case of compounds of formulae
I or II which are already appropriately substitutedO The
product of this r~action is then reacted with the said
salt of a non-coordinating anion.
In all cases, an immo~ile (heterogeneous) catalyst system
of high polymerization activity is obtained which can
advantageously be used for olefin polymerization.
The examples which follow are intended to illustrate the
invention in more detail.
~xample 1: Cl2ZrCp ( Cp-vinyl)
5.29 g (57.4 mmol) of 6-methylfulvene were dissolved in
100 cm3 of THF and 38~3 cm3 of a 1.5 M (57.43 mmol)
lithium diiQopropylamide/THF complex solution in cyclo-
hexane were added dropwise in the course of 1 h and the
mixture was stirred for 2 h at RT. After filtering, the
filtrate was evaporated and the Li~ (Cp-vinyl)e content
was determined by NMR spectroscopy and found to be about
85%; the remainder was adhering solvent.
The yield was 6.27 g (about 95%).

- 12 - 2 ~ J ~ r9
1.13 g ~85~ pura - 11.52 mmol) of ~i (Cp~vinyl),
dissolved in 30 cm3 o~ THF~ were added in the cour~e of
15 min at -78C ~o a suspen~ion of 3.03 g (11.53 mmol) of
Cl3CpZr in 30 cm3 of THF. A~ter warming to RT, the mixture
was stirred for a ~urther 3 h and ~he clear yellow
solution was evaporated. The re~idue was stirred wi~h 20
cm3 o~ n-pentane and the mixture evapoxated again. After
~tirring with toluene~ the mixture wa6 filteredl the
solvent was stripped off and n-pentane wa~ added and,
after digestion, stripped off. ~fter taking up in C~C13~
the mixture was filtered and the filtrate wa~ evaporated
and digested with n-pentane, whereupon the oily residue
solidified, and the product was filtered off and dried.
Yield: 2.38 g (7.48 mmol - 64.8%) of (Cp~Cp ~inyl)ZrCl2.
The product obtained had the NMR spectrum to be expected
(100 MHZ, CDCl3): ~ = 5-35 (ddt lH, JC1B = 11~ 38~ = lHz)~
5-58 (dd~ lH~ J~r~8 = 18 Hz), 6.33 - 6.53 (m, 9H, Cp-H),
6.58 (dd, lH).
Example 2: Homopolymerization of C12~rCp (Cp-vinyl)
0.34 g (1.07 mmol) of the complax from Example 1 were
dissolved in 10 cm3 of toluene, 0.1 g of ~ azo-i~o-
butyronitrile (AIBN) was added ~nd the mixture was
6tirred for 2 h at 90C. A greeni~h solid formed, which
was filtered off and washed with ~olvent. After drying,
0.11 g of product was obtained; the Zr content was 22.5~.
Example 3: Hompolymeri~akion of Cl2ZrCp(Cp-vinyl)
0.25 g (0.79 mmol) o~ the complex from Example 1 wa~
di~solved in 10 cm3 o~ toluene, 0.1 g of AIBN wa~ added
and the mixture was stirred for 4 h at 100C; after
adding a further 0.1 g of AIBN, the mixture was ~tirred
for a further 6 h at this temperature and the bxowni~h
precipitate was filtered off, washed and dr~ed. Th~
0.18 g of product contained 24% Zr.
~xample 4: C12Zr (Cp-vin~l)z
1.54 g (85% pure - 14 mmol) of Li(Cp-vinyl) in lO0 cm3 of
THF were added in portions at -78C to 2.58 g (6.B4 mmol)

- 13 - 2 ~ 9~ 2
of Cl4Zr(thf )2 in 50 cm3 of ~HF. After warming to 20C,
the solvent was stripped o~f in the course of 1 h at RT.
The yellow-orange evaporation residu0 was extracted with
a total of 300 cm3 of n-hexane/toluene 2:1 (vol) in port-
ions and the extracts were filtered of~ and evaporated.n-Pentane and a few cm3 of toluene were added to the
residue and after filtering, ~he filtra~e ~a~ evaporated
and extracted with a little n-pentane. A whitish residue
remains, which was dried under vacuum.
Yield: 0.37 g (1.03 mmol - 15%) of ~Cp vinyl)2ZrCl2
~he compound had the correct elementary analysi~.
Ex~mple 5: Me2ZrCp(Cp-vinyl)
1.75 cm3 of a 1.6 N (2.8 mmol) ethereal methyllithium
solution were added dropwise at -50C to 0.4 g
(1.26 mmol) of the complex from Example 1 in 10 cm3 of
Et2O and the mixture was stirred for 1 h at 0C. After
replacing the solvent by n-pentane, the mixture was
stirred for a further 1 h at RT and evaporated and the
residue was extracted with toluene. A white evaporation
residue then remains.
Yield: 0.2 g (0.72 mmol - 57%) of (Cp)~Cp vinyl)ZrMe2.
The NMR sp~ctrum shows the integration ratio of 2:1 to be
expected for aromatic compounds - to saturated hydro-
carbon H.
Example 6: Cl2Zr(Me2,vinYl-CP)2~iMe2
1~.7 am3 of 1.6 N (20.3 mmol) ethereal methyllithium were
added dropwise to 3 g (10.~ mmol) of (2,3-Me2-5-vinyl-
C5~2)2SiMe2 in 50 cm3 of Et2O and the mixture was then
stirred for 2 h at about 35C. The solvent was then
stripped off. 2.35 g (lO.1 mmol) of ZrCl4 were su~pended
in 100 cm3 of CH2CCl2 at -78C and the evaporation residue
described above was added to the su~pension. The mixture
was slowly warmed to 0C and stirred for 1 h at this
temperature and, aftex filtering, the solvent was
stripped off. The filtered and evaporated toluene extract
was examined by NMR spectroscopy. It shows a complex
, - - , . .

_ ~4
mixtuxe.
Yield: 0.87 g (2.19 mmol - 22~) of rac/meYo-{(2/3-Me2 5-
vinyl-C5H2)2SiMea}Zrcl2-
Example 70 Copolymerization of Cl2ZrCp(Cp-vinyl)
A mixture of 0.1 g (O.31 mmol) of the abovementioned
complex and 5 cm3 of vinylbenzene was stirred for 6 h at
60~C in 50 cm3 of toluene/n-hexane (1:4 by volume) with
the addition of 0.15 mg o AIBN. After very slight
formation of solid~ the mixture was evaporated, the
residue taken up several times in toluene and the solvent
stripped off again. The NMR ~pectrum of the final residue
~how~ no further vinyl groups.
Yield: 3.4 g of copo.lymer; Zr content: 0.88~.
Example 8: Terpolymerization of Cl2ZrCp(Cp-vinyl)
0.2 g (0.63 mmol) of the abovementioned complex, 0.5 cm3
of divinylbenzene and 8.5 cm3 of vinylbenzene were stirred
in 15 cm3 of toluene with 0.1 g of AIBN for 2 h at 80C.
After adding a further 20 cm3 of solvent, the gelatinous
mas~ was stirred for a further 3 h at this temperature.
After evaporation, the residue was washed thoroughly with
n-pentane and dried.
Yield: 4.57 gj Zr content 0.94%.
~xample 9: Terpolymerization of ClzZrCp(Cp-vinyl)
0.25 g (0.79 mmol) of the complex ~rom Example 1, 1 cm3
o~ divinylbenzene and 8.5 cm3 of vinylben~ene were stirred
in 15 cm3 of toluene with 0.1 g of A~BN at 80C. After
2 h, the gelatinous ma~s was diluted with 15 om3 of
toluene and ~tirred for a further 2 h at the above
temperature. The subsequent procedure corre~ponded to
that of Example 8.
Yield: 3.74 g, Zr content: 1.2%.
Example 10: Copolymerization of (Cp-vinyl)~ZrClz
0.2 g (0.56 mmol) of the abovementioned compound and
5 cm3 of vinylbenzene were ~tirred in 20 cm3 o~ toluene
with 0.1 g of AIBN at 75C for 5 h. After evaporation,

- 15 ~ J~
the resulking mas~ wa~ washed with n-penkane and dried.
-A little vinylbenzene was still discernible in the NMR
spectrum, but no vinyl ~ignals from the metallocene
compound.
Yield: 3 g; Zr content 1.5%.
Example 115 Terpolymerization of Me2ZrCp(CP-vinyl)
O.1 g (O.36 mmol) of the abovementioned complex, 0.5 cm3
of divinylbenzene and 5 cm3 of vinylbenzene were stirred
in 15 cm3 of toluene with 0.1 g of AIBN at 80C for 4 h.
The gelatinous product was filtered off, washed and
dried.
Yield: 3.7 g; Zr content: 0.7%.
Example 12:
Terpolymerization of [(2,3-M~2-5-vinyl-c5H2)2siNe2]Zrcl2
150.22 g (0.51 mmol) of the said complex, 1 cm3 of divinyl- i
benzene and 8 cm3 of vinylbenzene were stirred in 30 cm3
of toluene with 0.1 g of AIBN at 85~C for 7 h. After
evaporation and thorough washing of the residue with n-
pentane, the product was dried.
Yield: 4.2 g; 1~ Zr content.
Example 13:
Hompolymerization o~ Cl2ZrCptCp-vlnyl) without solvent
(by the aation oP heat)
0.2~ g (0.75 mmol) of the said compound was heated at
115C for 1 h in a Schlenk vessel. During this period the
substance a~sumes a darker color. The ~ubstance was then
extracted with toluene and filtered off. 0.19 g of
product having a ~r content of 23% was obtained.
Example 14:
Reaction of a metallocene polymer with a cocatalyet
2 g of th~ product from Example 11 were suspended in
10 cm3 of toluene and 0.13 g (O.15 mmol) of
~Bu3NH][B(C8F5)4] was added to the suspension at 0C and
the mixture wa~ stirred for 1 h. The supernatant was
removed from the dark colored mixture by decanting and
.

-- 16 --
the product was washed with ~olvent and then dried under
vacuum.
Yield: 1. 87 g; Zr content: 0 . 6% .
Ex~mple 15: Reaction of a metallocene polymer with an
alkylating agent and a cocatalyst
2 g of the product from Example 1~ were ~uspended in
25 cm3 of Bt20 and 0 . 4 cm3 of a 1.5 N (O.64 mmol) ethereal
MeLi 601ution was added at -20C, the mixture was 6tirred
for 1 h at 0C and filtered, the 601vent was replaced by
20 cm3 of toluene and ~.12 g (0.21 mmol~ of
~Bu3NH][B-(p-tolyl)4] was added. After 3tirring for 1 h,
the product was filtered off, washed and dried.
Yield: 0 . l9 g; Zr content: 1. 39~ .
Olefin polymerization using a metallocene monomer as
catalyst
Example 1 6
900 cm3 of a die~el oil fraction (b.p~: 10û-120C~ were
initially introduced into a 1.5 d~l3 reactor and heated to
70 C . The reactor was charged with 13 nunol of a 1096
strength toluene solution of methylaluminoxane and 1 ~,~mol
of catalyst 5from Example 1~. Ethylene wa~ then in~ected
until a f inal pre~ure of 7 bar wa~ reached a~d the
mixture wa~ pol~merized for 2 h. A~ueous HCl was then
added to ~he pol~nner solution. The polymer was isolated,
washed with acetone and dried under vacuum. 82 . 7 g o~
polyethylene were obtained, corresponding to an activity
of 41.4 kg of polymer/mmol Zr-h (see table for further
data ) .
Example 1 7
The procedure was as in Example 16. The polymeri~ation
catalyst conkained the metallocene monomer from Bxample
4 . 78 . 9 g of polymer were obtained. This corresponds to
a yield of 39.5 kg of polyethylene/mmol Zr-h ( see table
for further data).

- 17 ~
Ole~in polym~rizatlon uaing me~allocene polymera ~8
catalyst
Example 18
~he procedure was as in Example 16. ~he catalyst used wa~
the product from Example 7 ( O . 001 nanol Zr) . 72 g of
polyethylene were obtained, corresponding to 36 kg of
polymer/mmol Zr h (see table for further data~.
Example 1 9
The polymerization was carried out as in Example 16. The
amount of catalyst according to Example 10 which was
employed corresponded to 0 .0005 mmol Zr. 27.1 g of
polyethylene were obtained. This corresponds to 27.1 kg
of pol~mer/mmol Zr-h (see table for further data).
Example 20
The procedure was as in Example 16, except that the
catalyst from Example 8 was used (0.5 ~mol Zr). The yield
after 2 h wa~ 52.6 g of polyethylene having a VI of
620 cm3/g (see table).
Example 21
The procedure was a in Ex~mple 16, except that ths
catalyst from Example 9 was u~ed (0.2 ~mol Zr). Tha yield
after 2 h was 32 . 2 g of polyethylene having a VI of
671 cm3/g (see table).
Example 22
900 cm3 of a diesel oil fraction (b.p.: 100-120C~ and
0.015 g (corresponding to 0.001 mmol Zr) of catalyst from
Example 14 were initially introduced into a 1.5 dm3
reactor and heated to 70C. After injecting ethylene
until a final pressure of 7 bar was reached, poly-
merization was carried out for 2 h. After decomposition
with HCl, the product was washed with acetone and dried.
63.7 g of polyethylene were obtained, corresponding to
31.9 kg of polymer/mmol Zr-h (see table for further
data).

)J ~
Example 23
~he procedure was as in E~ample 22, but the ~ataly~t
originated from Example 15 and the yield of polyethylene
was 68.0 g. This corresponds to an actLviky of 34 g of
polymer/mmol ~r-h (see table for ~urther data~.
Example 24
After flushing with nitrogen, a dry 16 dm3 reactor was
filled with 10 dm3 of liquid propylene. 40 mmol of a
toluene solution of methylal~minoxane were then added and
the mixture was stirred for 15 min at 30C.
In parallel with this, a mixture of 0.05 mmol of metal-
locene according to Example 6 and 20 mmol of a toluene
solution of methylaluminoxane was prepared and pre-
activated by leaving to stand for 15 minutes.
This mixture was then added to the reactor, the reaction
mixture was heated to 70C and the polymerization was
started. After 1 h the reaction was stopped by cooling
and releasing pressure. 2.39 kg of polypropylene were
obtained. This corresponds to 47.8 kgJmmol Zr.h (eee
table for further data).
Example 25
The procedure was as in Example 24. Howevert the catalyst
u~ed wa~ 0.05 mmol o~ metallocene polymer according to
Example 12.
1.95 kg of polypropylene were obtained, corresponding to
39 kg of polymer/mmol Zr h ~see table for further data).
Example 26
80 cm3 of cyclopentane, diæsolved in 800 ml of diesel oil
(boiling point 100-120C), were initially introduced into
a 1. 5 dm3 reactvr and the reactor was charged with
60 mmol of a toluene solution of methylaluminoxane and
O.01 mmol of metallocene polymer according to Ex~mple 8.
After polymerization for 2 h at 60C, the reaction was

~topped u~ing methanol; ~he re~ulking polymer wa~ fil-
tered of~ and dried. The yield wa~ 6.2 g, corresponding
to 0.31 kg of polymer/mmol Zr-h.
Example 27
600 cm3 of a diesel oil fraction (b.p.s 100-~20C) and
300 cm3 of cyclopentene were initially introduced into a
1.5 dm3 reactor and heated to 60CO The reac~or was
charged with 60 mmol o~ a toluene solution of m~thyl-
aluminoxane and 0.01 mmol of metallocene polymer
according to Example 2. After in~ecting ethylene to a
pressure of 7 bar, the batch was polymerized for 2 h, the
polymer solution was then added to an acetone/methanol
mixture and the cyclopentene/ethylene copolymer was
isolated and dried. The yield was 97.6 g, corresponding
to 4.88 kg o~ copolymer/mmol Zr h (see table for further
data).
Example 28
A 1.5 dm3 polymerization reactor was flushed with nitro-
gen and then with ethylene and filled with a solution of
25 g of norbornene in 750 cm3 of toluene. The reactor was
then brought to 25C, with stirring, and 1 bar ethylene
was injected.
20 mmol of a toluene ~olution of methylaluminoxane were
then added to the reactor and the reaction mixt,ure was
~tirred ~or 15 min, the ethylene pressure being kepk at
1 bar by metering in further ethylene.
In parallel with this, 0.05 mmol of metallocene polymer
according to Example 12 were added to 10 mmol of the
toluene solution of methylaluminoxane and pre-actiYated
by leaving to stand for 15 minute~,
This mixture was th~n metered into the reactor and the
reaction mixture wa~ polymerized for 1 h at 25C~ with
stirring, the ethylene pressure being kept at 1 bar. The
contents were then run off into a vessel containing
, :

~ 20 =
100 cm3 o~ i~opropanol and 2 dm3 of acetone were added to
the mix~ure, the resulting mixture wa~ skirred or 10 min
and the ~uspanded polymer ~olid was ~eparated off. ~he
solid was then ~tirred for 2 h in an alkaline ethanol
solution and the polymer was filtered off and dried for
h at 80~C under vacuum. 19 g of copolymer were
obtained, corresponding to 0.3 kg/mmol Zr h (see table
for further data)
Abbreviations:
Cp = cyclopentadienyl ~e = methyl
THF = tetrahydrofuran Et = ethyl
MAO = methylaluminoxane R~r = room temperature
VI = ~iscosity index

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