AU640286B2

AU640286B2 - Process for the preparation of a high molecular weight olefin polymer

Info

Publication number: AU640286B2
Application number: AU87759/91A
Authority: AU
Inventors: Martin Antberg; Volker Dolle; Jurgen Rohrmann; Walter Spaleck; Andreas Winter
Original assignee: Hoechst AG
Current assignee: Hoechst AG
Priority date: 1990-11-12
Filing date: 1991-11-11
Publication date: 1993-08-19
Anticipated expiration: 2011-11-11
Also published as: EP0485822B1; DE59107973D1; CA2055216C; EP0485822A3; ES2091273T3; EP0485822A2; ZA918925B; JP3362153B2; AU8775991A; JPH04268307A; CA2055216A1

Description

AUSTRALIA

Patents Act 1990 P/00/01O 2/l 9 Regulation 3.2(2) 0~ 2 '0

ORIGINAL

COMPLETE SPECIFICATION STANDARD PATENT Application Number: Lodged: 0S 00

OS

*so Invention Title: PROCESS FOR THE PREPARATION OF A HIGH MOLECUTLAR WEIGHT OLEFIN POLYMER The following statement is a full description of this Invention, including the best method of performing it known to :-us HOECHST AKTIENGESELLSCHAFT HOE 90/F 334 Dr.LO/PP Description Process for the preparation of a high molecular weight olefin polymer The invention relates to a process for the preparation of olefin polymers having high isotacticity, a narrow molecular weight distribution and a high molecular weight.

Polyolefins having a high molecular weight are particularly important for the production of films, sheets or large hollow articles, such as, for example, pipes or moldings.

The literature discloses soluble metallocene compounds based on bis(cyclopentadienyl)zirconiumalkyl or halide in combination with oligomeric aluminoxanes. With these systems, ethylene and propylene can be polymerized with moderate activity, but isotactic polypropylene is not "*600. obtained.

o* a It is also known that the catalyst system bis(cyclopentadienyl)titaniumdiphenyl/methylaluminoxane is capable of 20 converting propylene into stereo block polymers, i.e.

polypropylene having longer or shorter isotactic sequences (cf. U.S. Patent 4,522,982). Substantial advantages of this catalyst system are the fact that the polymerization temperatures (0C to -60°C) are irrelevant on a large 25 industrial scale, and the completely unsatisfactory catalyst activities.

Isotactic polypropylene can be prepared with the aid of ethylenebis 5, 6,7-tetrahydro-1-indenyl) zirconium dichloride together with an aluminoxane in a suspension 30 polymerization (cf. EP-A 185 918). The polymer has a narrow molecular weight distribution, which is advantageous for certain applications, for example for highperformance injection molding.

-2- At the same time, the catalyst system has a number of deficiences.

The polymerization is carried out in toluene, which has to be purified by an expensive procedure and freed from moisture and oxygen. Furthermore, the bulk density of the polymer is too low and the particle morphology and the particle size distribution are unsatisfactory.

However, a particular disadvantage of the known process is that, at polymerization temperatures of interest industrially, it is possible to prepare only polymers having an unacceptably low molecular weight.

A special preactivation method for the metallocene with an aluminoxano was also proposed, which method leads to a considerable increase in the activity of the catalyst system and to a substantial improvement in the particle morphology of the polymer (cf. DE 37 26 067). Although the preactivation increases the molecular weight, no substantial increase can be achieved.

A further, but still insufficient increase in the molecu- .*20 lar weight can be realized by using specially hetero atom-bridged metallocenes having high metallocene activity (EP-A 0 336 128).

Catalysts based on ethylenebisindenylhafnium dichloride and ethylenebis(4,5,6,7-tetrahydro-l-indenyl)hafnium dichloride and methylaluminoxane are also known, by means floss*: of which relatively high molecular weight polypropylenes 0 can be prepared by suspension polymerization (cf. J.A.

Ewen et al., J. Am. Chem. Soc. 109 (1987), 6544). Among industrially relevant polymerization conditions, however, the particle morphology of the polymers thus produced is "unsatisfactory and the activity of the catalysts used is comparatively low. In conjunction with the high catalyst costs, economical polymerization is thus impossible with S these systems.

3 It was the object to find a catalyst which produces polymers having good particle morphology and a high molecular weight in a high yield.

It was found that this object can be achieved using bridged metallocene systems substituted in a certain manner in the ligand sphere.

The invention thus relates to a process for the preparation of olefin polymers by polymerization or copolymerization of an olefin of the formula Ra-CH=CH-R b wherein Ra and Rb are identical or different and are a hydrogen atom or a hydrocarbon radical having 1 to 14 C atoms, or R a and

R

b together with the atoms binding them, may form a ring, at a temperature of -60 to 200 0 C, at a pressure of 0.5 to 100 bar, in solution, in suspension or in the gas phase, in the presence of a catalyst which is composed of a metallocene as the transition metal compound and an aluminoxane of the formula (II) R14 R14

R

0* R R 14 Al Al 0- I I

A

SR

14

R

14 :0.

0 for \e linear type and/or of the formula III

R

14

(II

Al 0 p+2 for the cyclic type, 00 wherein, in the formulae (II) and (III), the radicals R' 4 may be identical or different and are a Cl-C 8 -alkyl group, a C 6 -C,,-aryl group or hydrogen, and p is an integer of from 2 to 50, wherein the metallocene is a compound of the formula I 9 4 (CR R n

.R

M1 R6 R R2 R R i 9 R4(CR8R9) n wherein

M

1 is a metal of group IVb, Vb or VIb of the Periodic Table,

R

1 and R 2 are identical or different and are a hydrogen atom, a C 1

-C

1 -alkyl group, a Ci-Co 1 -alkoxy group, a C-Cl 1 -aryl group, a C 6 -Co 1 -aryloxy group, a C2-CIoalkenyl group, a C 7

-C

40 -arylalkyl group, a C7-C4oalkylaryl group, a C 8

-C

40 -arylalkenyl group or a .10 halogen atom,

S..

R

3 and R 4 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -Co 1 -alkyl group which may be halogenated, a C-Co 1 -aryl group, an -NR 2 10

-SR

10 -OSiR 3 10 -SiR 3 1 0 or -PRZ 10 radical, wherein is a halogen atom, a Ci-Co 1 -alkyl group or a C-Co 1 -aryl group,

R

5 and R 6 are identical or different and have the meaning stated for R 3 and R 4 with the proviso that R 5 and R 6 are not hydrogen,

S

R

7 is R11 R 11

R

1 1 R R 1 1 Rl R RI R M2 M 2

M

2 2 (CR 2 13) 2 R12 R12 R12 R12 R12 11 R11 R R C M2 R12 R12

=BR

1 =A1R 11 =SO, =SO 2

=CO,

=PR

1 or =P(O)R 1 wherein

R

1

R

12 and R13 are identical or different and are a hydrogen atom, a halogen atom, a Cl-Co 1 -alkyl group, a C 1 Cl-fluoroalkyl group, a C 6

-C

1 o-aryl group, a C 6

-C

1 ofluoroaryl group, a CI-Co 1 -alkoxy group, a Cz-Cloalkenyl group, a C 7

-C

40 -arylalkyl group, a C 8

-C

40 10 arylalkenyl group or a C 7

-C

4 o-alkylaryl group, or R 1 and R 12 or R 1 and R 13 together with the atoms binding them, each form a ring,

M

2 is silicon, germanium or tin,

R

8 and R 9 are identical or different and have the meaning stated for R 1 and e: m and n are identical or different and are zero, 1 or 2, m plus n being zero, 1 or 2.

Alkyl is straight-chain or branched alkyl. Halogen (halogenated) is fluorine, chlorine, bromine or 20 iodine, preferably fluorine or chlorine.

The present invention furthermore relates to the poly- Solefins prepared by the process described.

I -6- The catalyst to be used for the process according to the invention is composed of an aluminoxane and a metallocene of the formula I 0 1 C 8R9 RC

R

R /11

R

lz R 4t(CR 89 In the formula 1, MW is a metal of group IVb, Vb or VIb of the Periodic Table, for example titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, preferably zirconium, hafnium or titanium.

R' and R 2 are identical or dif ferent and are a hydrogen *'atom, a Cl-C 1 -alkyl group, preferably a Cl-C-alkyl group, a Cl-Clo-alkoxy group, preferably a C-C 3 -alkoxy group, a

:C

6 -Cl-aryl group, preferably a C-Ce-aryl group, a eco 0 0* aryloxy group, preferably a C 6 -C.C-aryloxy group, a C 2

-CIO-

0 "15 alkenyl group, preferably a C 2 -C4-alkenyl group, a C7-C 40 arylalkyl group, preferably a C 7 -C-arylalkyl group, a C 7

C

40 -alkylaryl group, preferably a C 7

-C

12 -alkylaryl group, #foe*:a c-C 40 -arylalkenyl group, preferably a C.-C 12 -arylalkenyl 4 a group, or a halogen atom, preferably chlorine.

6 20 R 3 and R 4 are identical or different and aro a hydrogen 60 atom, a halogen atom, pr~eferably a fluorine, chlorine or S00# 0 a bromine atom, a C 1 -Clo-alkyl group, preferably a C,-CA'alkyl group, which may be halogenated, a C.-C 1 -aryl 0 group, preferably a 0 6 ,-Ce-aryl group, an -NR 2 ,I -SR" 0 25 -OSiR 3 10 -SiR 3 10 or -PR 2 10 radical, wherein R 10 is a halogen atom, preferably a chlorine atom, or a C 1 -Cl-alkyl group, -7preferably a Cl-C 3 -alkyl group, or a C 6 -Cl-aryl group, preferably a C 6

-C

8 -aryl group. R3 and R 4 are particularly preferably hydrogen.

R 5 and R 6 are identical or different, preferably identical, and have the meanings described f or R 3 and R with the proviso that R 5 and R 6 may not be hydrogen. R's and R 6 are preferably (C,-C 4 )-alky. which may be halogenated, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl or trifluoromethyl, in particular methyl.

k 7 is Ril R 11

R

11 iRl M 2 (CR 2 13 2 0 112 1 R 12 1 1

I

'12 1 oB11 Ar11 G -S-1 =SO, =So 2 f =NR 11

=CO,

=PR. wherein R' 2 and R" 3 are identical or Va different and are a hydrogen atom, a halogen atom, a Cj-

C

1 0 -alkyl group, preferably a Cl-C 4 -alkyl group, in paris8 1 ticular a methyl group, a C 1

-C

1 0 -fluoroalkyl group, preferably a CF 3 group, a C 8

-C

1 -aryl group, preferably a CB-C-aryl group, a C 6

-C

1 -fluoroaryl group, preferably a pentafluorophenyl group, a C 1

-C

1 -alkoxy group, preferably too%*:a C-C 4 -alkoxy group, in particular a niethoxy group, a C 2 CI-alkenyl group, preferably a C 2

-C

4 -alkenyl group, a C 7 C,-ayaly grupeeal4 7COayaklgop aC.-C-arylalkeyl group, preferably a CS-C 1 2-arylalk goup gr:oup, or a C 7

-C

40 -a3kylaryl group, pr~eferably a C7-C1 2 *8alkylaryl group, or R 11 and R 1 2 or R" and R1 3 together with the atoms bindinq thei, ep-.*Il form a ring.

e 2 is silicon, germanixan or tin, preferably silicon or germanium.

R 7 is preferably =CR"R' 2 =SiRl 1

R

12 I =GjeR 1R 1 2 =SO, =PR" or

R

8 and R 9 are identical or different and have the meaning stated for R" 1 m and n are identical or different and are zero, 1 or 2, preferably zero or 1, m plus n being zero, 1 or 2, preferably zero or 1.

The particularly preferred metallocenes are thus the compounds of the formulae A, B and C R

RQR

(),R11

R,

R 1 1

R

1 2 C R R66 04e 0 4R .4 9 in which

M

1 is Zr or Hf, R 1 and R 2 are methyl or chlorine, R 5 and R 6 are methyl, ethyl or trifluoromethyl and R 8

R

9

R

1 and R 12 have the abovementioned meanings, in particular the compounds I mentioned in the Illustrative Examples.

The chiral motallocenes are used as a racemate for the preparation of highly isotactic poly-l-olefins. However, it is also possible to use the pure R or S form. Optically active polymers can be prepared with these pure stereoisomeric forms. However, the meso form of the metallocenee should be separated off, since the center which is active in polymerization (the metal atom) is no longer chiral in these compounds owing to mirror symmetry at the central metal and therefore cannot produce the highly isotactic polymer. If the meso form is not separated off, an atactic polymer is formed in addition to isotactic polymers. For certain applications for example flexible moldings this may be quite desirable.

The separation of stereoisomers is known in principle.

20 The metallocenes described above can be prepared according to the following reaction scheme: c

H

2 Rc ButylLi HRCLi X-(CR-R 9 )mR 7

(CR

8

R

9 )n-X

H

2 Rd ButylLi HRdi HRc CRR 9 1,-R 7

-(CRBR

9 -RdH 2 Butyl Li S. LiRc-(CR 8

R

9 )m.-R 7 (CRR)n-RdLi Mi 6

(RR

9 C)m R c (RRC)m Rc

SR

7

M

1

R

1 Li R 7 I I I Cl G:

(RR

9 C)n Rd (RRC)n Rd 10

R

2 Li4

R

7

(R

8 R

C)

Rc I R i

M

1 R2

R

d X Cl, Br, I, O-Tosyl; 3

H

2 Rc o H2R d

SQS

S S *0 S We S p 56. S 6*

S

gee e

SOS

55

S

The preparation processes are known from the literature; cf. Journal of Organometallic Chem. 288 (1985) 63-67, EP-A 320 762 and the Illustrative Examples.

According to the invention, the cocatalyst used aluminoxane of the formula (II) is an S 6 05 Se 5 See.

0* 5* 0

S

e S@ S SO e

S

see...

S

*5S5*5 0

R

14 SAl O

R

1 4 R1---A

R

1 4

(II)

for the linear type and/or of the formula (III)

R

14 -0 Al-

(III)

for the cyclic type, wherein, in the formulae (II) and (III), the radicals R 14 may be identical or different and are a C,-C.-alkyl group, a Ce-C.,-aryl group or hydrogen, and p is an integer of from 2 to 50, preferably from to The radicals R 14 are preferably identical and are methyl, 11 isobutyl, phenyl or benzyl, particularly preferably methyl.

If the radicals R 14 are different, they are preferably methyl and hydrogen or alternatively methyl and isobutyl, hydrogen or isobutyl preferably being present in an amount of 0.01-40% (number of radicals R14).

The aluminoxane can be prepared in various ways by known processes. One of the methods comprises, for example, reacting an aluminum-hydrocarbon compound and/or a hydridoaluainum-hydrocarbon compound with water (gaseous, solid, liquid or bound for example as water of crystallization) in an inert solvent (such as, for example, toluene). For the preparation of an aluminoxane having different alkyl groups R 1 two different aluminumtri- 15 alkyls (AlR 3

AIR'

3 are reacted with water, depending on the desired composition (cf. S. Pasynkiewicz, Polyhedron 9 (1990) 429 and EP-A 302 424).

o The exact structure f the aluminoxanes II and III is not known.

Regardless of the method of preparation, the common a feature of all aluminoxane solutions is a changing content of unconverted aluminum starting compound, which is present in free form or as an adduct.

g* It is possible to preactivate the metallocene before use in the polymerization reaction with an aluminoxane of the formula (II) and/or (III). This substantially increases the polymerization activity and improves the particle morphology.

The preactivation of the transition metal compound is carried out in solution. The metallocene is preferably dissolved in a solution of the aluminoxane in an inert hydrocarbon. A suitable inert hydrocarbon is an aliphatic or aromatic hydrocarbon. Toluene is preferably used.

12 The concentration of the aluminoxane in the solution is in the range from about 1% by weight to the saturation limit, preferably from 5 to 30% by weight, based in each case on the total solution. The metallocene may be used in the same concentration, but is preferably employed in an amount of 10-4 1 mol per mol of aluminoxane. The preactivation time is 5 minutes to 60 hours, preferably from 5 to 60 minutes. It is carried out at a temperature of -78 0 C to 100 0 C, preferably 0 to 70 0

C.

The metallocene can also be prepolymerized or applied to a carrier. For prepolymerization, the olefin used in the polymerization, or one of the olefins used in the polymerization, is preferably used.

Suitable carriers are, for example, silica gels, aluminas, solid aluminoxane or other inorganic carriers.

Another suitable carrier is a polyolefin powder in finely divided form.

0o S C

SC

A further possible embodiment of the process according to the invention comprises using a salt-like compound of the formula RxNH 4

BR'

4 or of the formula R 3

PHBR'

4 as a cocatalyst, instead of or in addition to an aluminoxane. In the formulae, x is 1, 2 or 3, the radicals R are identical or different and are alkyl or aryl and R' is aryl which may also be fluorinated or partially fluorinated. In this :25 case, the catalyst is composed of the reaction product of a metallocene with one of the stated compounds (cf.

EP-A 277 004 and the Preparation Examples C and F).

To remove catalyst poisons present in the olefin, purification with an aluminumalkyl, for example AlMe 3 or AlEt 3 is advantageous. This purification may be carried out in the polymerization system itself, or the olefin is brought into contact with the Al compound prior to addition to the polymerization system and is then separated off again.

The polymerization or copolymerization is carried out in 13 a known manner in solution, in suspension or in the gas phase, continuously or batchwise, in one or more stages, at a temperature of 0 to 150 0 C, preferably 30 to 80 0

C.

Olefins of the formula Ra-CH=CH-Rb are polymerized or copolymerized. In this formula, R" and Rb are identical or different and are a hydrogen atom or an alkyl radical having 1 to 14 C atoms. However, R a and Rb, together with the C atoms binding them, may also form a ring. Examples of such olefins are ethylene, propylene, 1-butene, 1-hexene, 4-methyl-l-pentene, 1-octene, norbornene or norbornadiene. In particular, propylene and ethylene are polymerized.

If required, hydrogen is added as a molecular weight regulator. The total pressure in the polymerization 15 system is 0.5 to 100 bar. Polymerization in the industrially particularly interesting pressure range from 5 to 64 bar is preferred.

The metallocene is used here in a concentration, based on the transition metal, of 10 3 to 10-8, preferably 10-4 to 10 7 mol of transition metal per dm 3 of solvent or per dm 3 of reactor volume. The aluminoxane is used in a concentration of 10-5 to 10-1 mol, preferably 10 4 to 10- 2 mol, per dm of solvent or per dm 3 of reactor volume. In principle, however, higher concentrations are also possible.

25 If the polymerization is carried out as a suspension or solution polymerizatio:, an inert solvent conventionally used for the Ziegler low pressure process is employed.

For example, the reaction is carried out in an aliphatic or cycloaliphatic hydrocarbon; butane, pentane, hexane, heptane, isooctane, cyclohexane and methylcyclohexane may be mentioned as examples of these.

A gasoline or hydrogenated diesel oil fraction may furthermore be used. Toluene can also be used. Polymerization is preferably carried out in the liquid monomer.

14 If inert solvents are used, the monomers are metered in as a gas or liquid.

The polymerization can be carried out for any desired time, since the catalyst system to be used according to the invention shows only a slight time-dependent decrease in the polymerization activity.

In the process according to the invention, the metallocenes described produce polymers Laving a high molecular weight, high stereospecificity and good particle morphology in the industrially interesting temperature range between 30 and 80 0

C.

In particular, the zirconocenes according to the invention provide a molecular weight range which, in the prior art, was provided only by the hafnocenes. However, these 15 have the disadvantage of only low polymerization activity and very high catalyst costs, and the polymers prepared So.. therewith had a poor powder morphology.

*e The Examples which follow are intended to illustrate the invention in more detail.

0 a '25 S. r' .4

S

VN

MI

S/Mn m.p.

II

BD

MFI

Viscosity number in cm 3 /g Weight average molecular weight in g/mol Molecular weight dispersity c ielting point determined by heating/cooling rate) Isotactic index (II mm+1/2 mr) "C-NMR spectroscopy Polymer bulk density in g/dm 3 (230/5) Melt flow index, measured DIN 53,735, in g/10 min )etermined by jel permeation 3hromatography DSC (20 0 C/min determined by according to Synthesis of the metallocenes used in the Examples: 15 Starting substances: The preparation of the indenyls H 2 Rc and H 2 Rd used as starting compounds is carried out according to or analogously to: J. Org. Chem., 49 (1984) 4226-4237, J. Chem. Soc., Perkin II,-1981, 403-408, J. Am. Chem. Soc., 106 (1984) 6702, J.

Am. Chem. Soc., 65 (1943) 557, J. Med. Chem., 30 (1987) 1303-1308, Chem. Ber. 85 (1952) 78-85.

The preparation of the chelate ligands LiR c -(CR'Rg 9 )-R7-(CR 8

R

9 )n-RdLi is described in principle in: Bull. Soc. Chim., 1967, 2954, J. Am. Chem. Soc., 112 (1990) 2030-2031, ibid. 110 (1988) 6255-6256, ibid. 109 (1987), 6544-6545, J. Organomet. chem., 322 (1987) 65-70, New. J. Chem. 14 (1990) 499-503.

15 I) Synthesis of 2-Me-indene 110.45 g (0.836 mol) of 2-indanone were dissolved in 500 cm 3 of diethyl ether, and 290 cm 3 of 3 N (0.87 mol) ethereal methylgrignard solution were added dropwise so that gentle refluxing occurred. After boiling for 2 20 hours with a gentle refluxing, the mixture was poured onto an ice/hydrochloric acid mixture and adjusted to pH 2-3 with ammonium chloride. The organic phase was separated off, washed with NaHCO 3 and sodium chloride solution and dried. 98 g of crude product (2-hydroxy-2methylindane) were obtained, which was not further purified.

This product was dissolved in 500 cm 3 of toluene and heated with 3 g of p-toluenesulfonic acid under a water separator until the elimination of water was complete, the mixture was evaporated down, the residue was taken up in dichloromethane, the solution was filtered over silica gel and the filtrate was distilled in vacuo (80°C/10 mbar).

Yield: 28.49 g (0.22 mol-26%).

16 The synthesis of this compound is also described in: C.F. Koelsch, P.R. Johnson, J. Am. Chem. Soc., 65 (1943) 567-573 II) Synthesis of (2-Me-Indene) 2 SiMe 2 13 g (100 mol) of 2-Me-indene were dissolved in 400 cm 3 of diethyl ether, and 62.5 cm 3 of 1.6 N (100 mmol) of n-butyllithium/n-hexane solution were added dropwise in the cource of 1 hour while cooling with ice, after which stirring was continued for 1 hour at ~35 0

C.

6.1 cm' (50 mmol) of dimethyldichlorosilane in 50 cm 3 of EtgO were initially taken, and the lithio salt solution was added dropwise in the course of 5 hours at 0°C, stirring was carried out overnight at room temperature and the mixture was allowed to stand over the weekend.

15 The solid which had settled out was filtered off and the filtrate was evaporated to dryness. After extraction with small portions of n-hexane, filtration was carried out and the filtrate was evaporated down. 5.7 g (18.00 mmol) of white crystals were obtained. The mother •:20 liquor was evaporated down and then purified by column chromatography (n-hexane/H 2 CCl 2 9 i parts by volume), 2.5 g (7.9 mmol 52%) of product being obtained (as an isomer mixture).

r (SiO 2 n-hexane/H 2 CClz 9 1 parts by volume) 0.37 The 'H-NMR spectrum shows the signals to be expected for an isomer mixture, in shift and integration ratio.

III) Synthesis of (2-Me-Ind) 2

CH

2

CH

2 3 g (23 mmol) of 2-Me-indene were dissolved in 50 cm 3 of THF, 14.4 cm 3 of 1.6 N (23.04 mmol) n-butyllithium/ n-hexane solution were added dropwise and stirring was then carried out for 1 hour at 65°C. Thereafter, 1 ml -17 (11.5 mmol) of 1,2-dibromoethane was added at -78 0 C, and the mixture was allowed to warm to room temperature and was stirred for 5 hours. It was evaporated down and then purified by column chromatography (SiO 2 n-hexane/H 2 CCl 2 9 1 parts by volume).

The product-containing fractions were combined and evaporated down, the rosidue was taken up in dry ether, the solution was dried over MgSO 4 and filtered and the solvent was stripped off.

Yield: 1.6 g (5.59 mmol 49%) of isomer mixture rp (SiO 2 n-hexane/H 2 CCl 2 9 1 parts by volume) 0.46 The 'H-NMR spectrum meets the expectation for an isomer mixture in signal shift and integration.

A) Synthesis of rac-dimethylsilyl(2-Me-1-indenyl) 2 zirconium dichloride 1.68 g (5.31 mmol) of the chelate ligand dimethylsilyl(2methylindene), were added to 50 cm 3 of THF, and 6.63 cm 3 of a 1.6 N (10.61 mmol) n-BuLi/n-hexane solution were added dropwise. The addition was carried out at ambient 20 temperature in the course of 0.5 hour. The mixture was stirred for 2 hours at about 35°C, after which the solvent was stripped off in vacuo, the residue was stirred with n-pentane and the solid was filtered off and dried.

The dilithio salt thus obtained was added at -78 0 C to a 25 suspension of 1.24 g (5.32 mmol) of ZrCl 4 in 50 cm 3 of CH2Clz and the mixture was stirred for 3 hours at this temperature. After warming up to room temperature overnight, the mixture was evaporated down. The 'H-NMR spectrum indicated a rac-meso mixture in addition to the presence of a little zrCl4(thf) 2 After stirring with npentane and drying, the solid, yellow residue was suspended in THF, filtered off and investigated by NMR spectroscopy. These three operations were repeated several 18 times; finally 0.35 g (0.73 nmmol-14%) of product was obtained, in which, according to 1 H.-NMR, the rac f orm had been concentrated to more than 17 1.

The compound gave a correct elemental analysis and the following NMR signals (CDCl 3 100 MHz) 6 1. 25 6H1, Si-Me); 2.18 6H, 2-Me), 6.8 2H1, 3-11-Id); 6.92- 7.75 (in, 8H, 4-7-11-Id).

B) Synthesis of rac-diinethylsilyl(2-Me-1-inienyl) 2 z irc oniuzudiinethyl 1.3 cm 3 of a 1.6 N (2.08 minol) ethereal MeLi solution were added dropwise to 0.14 g (0.58 nimol) of rac-dlimethylsilyl (2-Me-l-indenyl) 2 Zirconium dichloride in 40 cm 3 of Et 2

O

0* at -50'C, and stirring was carried out for 2 hours at 0 00 10 0 C. After exchanging the solvent for n-pentane, stirring was continued for a further 1.5 hours at room temperature and the filtered residue was sublimed in vacuo. 0.19 g (0.44 minol-81%) cf sublimate with a correct elemental analysis was obtained.

C) Reaction of rac.-dimethylsilyl(2-Me-1-indenyl) 2 zirconiuindimethyl with [Bu 3 NH] [B(C 6

H

5 4J 0.17 g (0.39 nimol) of rac-dixmfthylsilyl(2-Me-1-indenyl) 2 zirconiumdiinethyl was added at 0 0 C to 0.18 g (0.36 nimol) O0of (Bu 3 NH][B(CrH 5 4 in 25 cm 3 Of toluene. The mixture was 0 WO 00warmed up to ambient temperature while stirring for one 25 hour. The deeply coloured mixture was then evaporated to a dryness.

0:60 An aliquot part of the reaction mixture was used for the polymerization.

D) Synthesis of rac -ethylene (2 -Me-1I- indenyl) 2 z irc onium dichloride 14.2 cm 3 of 2.5 N (35.4 nimol) n-BuLi/n-hexane solution 19 were added Aropwise to 5.07 g (17.7 mmol) of the ligand ethylene(2-,.:thylindene) 2 in 200 cm 3 of THF at room temperature in the course of 1 hour, and stirring was then carried out for 3 hours at about 50 0 C. A precipitate which was formed in the meantime goes into solution again. The solution was allowed to stand overnight.

6.68 g (17.7 mmol) of ZrCl,(thf) 2 in 250 cm 3 of THF were added dropwise, simultaneously with the above dilithio salt solution, to about 50 cm 3 of THF at 50C, and stirring was then carried out for 20 hours at this teni)erature. The toluene extract of the evaporation residue was evaporated down. After extraction of the residue with a small amount of THF, recrystallization was effected from toluene. 0.44 g (0.99 mmol-5.6%) of product was *15 obtained, the rac form having been concentrated to more than 15 1.

e The compound gave a correct elemental analysis and the S following NMR signals (CDC1 3 100 MHz): 6 2.08 (2s, 6H, 2-Me); 3.45-4.18 4H, -CH 2

CH

2 6.65 (2H, 3-H-Ind); 7.05-7.85 8H, 4-7-H-Ind).

E) Synthesis of rac-ethylene( 2-Me-l-indenyl) 2 zirconiuimdimethyl f 1.5 cm 3 of a 1.6 N (2.4 mmol) ethereal MeLi solution were added to 0.31 g (0.68 mmol) of rac-ethylene(2-Me-1indenyl) 2 zirconium dichloride in 40 cm 3 of Et 2 O, and stirring was carried out for 2 hours at -40 0 C. After exchanging the solvent for n-pentane, stirring was carried out for 1.5 hours at ambient tumperature and the mixture was filtered and the filtrate evaporated down.

0.22 g (0.54 mmol-80%) of sublimate with the correct elemental analysis was obtained.

F) Reaction of rac-ethylene(2-Me-1-indenyl) 2 zirconiumdimethyl with Bu 3 NH)[B(p-tolyl)4] 20 0.13 g (0.32 mmol) of rac-ethylene(2-methyl-l-indenyl) 2 zirconiumdimethyl was added to 0.16 g (0.28 mmol) of [Bu 3 NH][B(p-tolyl) 4 in 20 cm 3 of toluene and stirring was carried out for 1 hour at ambient temperature. The solvent was stripped off and drying was then carried out in vacuo.

An aliquot part of the reaction mixture was used for the polymerization.

Example 1 A dry 24 dm 3 reactor was flushed with nitrogen and filled with 12 dm 3 of liquid propylene.

35 cm 3 of a solution of methylaluminoxane in toluene (corresponding to 52 mmol of Al, mean degree of oligomerization n 17) were then added and the batch was stirred "'15 at 30°C for 15 minutes.

6 *e At the same time, 6.9 mg (0.015 mmol) of rac-ethylene(2- Me-l-indenyl) 2 zirconium dichloride were dissolved in 13.5 cm 3 of a solution of methylaluminoxane in toluene mmol of Al) and preactivated by allowing the solution to stand for 15 minutes.

a *0 The solution was then introduced into the reactor and heated to 70°C by supplying heat (10°C/min) and the polymerization system was kept at 70 0 C for 1 hour by cooling. The polymerization was stopped by allowing the excess gaseous monomer to escape. 1.56 kg of propylene were obtained. The activity of the metalloceno was thus 226 kg of PP per g of metallocene per h.

VN 67 cm 3 M, 58,900 g/mol; M,/Mn 2.0; II 95.9%; BD 350 g/dm 3 21 Example 2 Example 1 was repeated, except that 10.1 mg (0.023 mmol) of metallocene were used and oolymerization was carried out at 50 0

C.

0.51 kg of polymer powder were obtained, corresponding to a metallocene activity of 50.5 kg of PP per g of me'tallocene per h.

VN 10,' cm 3 M, 108,500 g/mol; M /Mn 2.2; II 96.4%; MFI (230/5) 210 g/10 min Example 3 Example 1 was repeated, except that 10.5 mg (0.023 mmo?) of the metallocene were used and polymerization was carried out at 30 0 C for 10 hours.

S

1.05 kg of polymer powder were obtained, corresponding to 15 a metallocene activity of 10.0 kg of PP per g of metallocene per h.

VN 124 cm3/g; M, 157,000 g/mol; /M14n 2.2; II 96,3%; MFI (230/5) 104 g/10 min Comparative Examples A C Polymerization was carried out analogously to Examples 1 to 3, using the metallocene rac-ethylenebisindenylzirconium dichloride. The viscosity numbers and molecular weights of the resulting polymer products were: Comparative Polym. temp. VN M, Example [cmn/g] [g/mol] A 70 30 19,900 B 50 46 38,500 C 30 60 48,700 22 These Comparative Examples show the effect of the substituent in the 2-position on the indenyl ligand in respect of increasing the molecular weight.

Example 4 The procedure in Example 1 was followed, except that mg (0.008 mmol) of rac-dimethylsilyl(2-methyl-lindenyl) 2 zirconium dichloride were used. The metallocene activity was 293 kg of PP per g of metallocene per h.

VN 171 cm 3 M, 197,000 g/mol; M /Mn 2.5; II 96.0%; MFI (230/5) 43.2 g/10 min; BD 460 g/dm3; m.p.

145 0

C

Example The procedure in Example 1 was followed, except that 6.0 mg (0.013 mmol) of rac-dimethylsilyl(2-methyl-1indenyl) 2 zirconium dichloride were used.

The polymerization temperature was 60°C and the polymerization time was 1 hour. The metallocene activity was 178 kg of PP per g of metallocene per h.

VN 217 cm 3 M. 297,000 g/mol; 2.3; II 96.4%; MFI (230/5) 12.9 g/10 min; m.p. 148 0

C

*S

Example 6 0000SS The procedure in Example 1 was followed, except that 2.4 mg (0.0052 mmol) of raee-dimethylsilyl(2-methyl-lindenyl) 2 zirconium dichloride were used. The polymeriza- 25 tion temperature was 50°C and the polymerization time was 3 hours. The metallocene activity was 89 kg of PP per g of metallocene per h.

VN 259 cm3/g; M 342,5C g/mol; M,/Mn 2.1; II 96.8%; MFI (230/5) 8.1 g/10 min; m.p. 150°C 23 Example 7 The procedure in Example 1 was followed, except that 9.9 mg (0.021 mmol) of rac-dimethylsilyl(2-methyl-1indenyl) 2 zirconium dichloride were used.

The polymerization temperature was 30 0 C and the polymerization time was 2 hours. The metallocene activity was 26.5 kg of PP per g of metallocene per h.

VN 340 cm 3 M, 457,000 g/mol; M, /Mn 2.4; II 96.0%; MFI (230/5) 2.5 g/10 min; m.p. 153 C Example 8 A dry 24 dm 3 reactor was flushed with nitrogen and filled with 6 dm 3 of a gasoline cut from which aromatics had been removed and which had a boiling range of 100-120°C and 6 dm 3 of liquid propylene. 35 cm 3 of a solution of methylaluminoxane in toluene (corresponding to 52 mmol of Al, mean degree of oligomerization n 17) were then added and the batch was stirred at 300C for 30 minutes.

At the same time, 14.7 mg (0.031 mmol) of rac-dimethylsilyl(2-methyl-l-indenyl) 2 zirconium dichloride were dissolved in 13.5 cm 3 of a solution of methylaluminoxane in toluene (20 mmol of Al) and preactivated by allowing the solution to stand for 30 minutes.

The solution was then introduced into the reactor and the polymerization system was kept at 50 0 C for 1 hour by cooling. The polymerization was stopped by adding 50 cm 3 of isopropanol. The metallocene activity was 159.2 kg of PP per g of metallocene per h.

6 VN 188 cm 3 M4 240,000 g/mol; M 4 2.1; II 96.0%; MFI (230/5) 28.6 g/10 min; m.p. 149 0

C

24 Example 9 Example 8 was repeated, except that 15.2 mg (0.032 mmol) of the metallocene were used, the polymerization time was 2 hours and the polymerization temperature was 30 0

C.

The metallocene activity was 24.1 kg of PP per g of metallocene per h.

VN 309 cm 3 M, 409,000 g/mol; M,/Ml 2.3; II 97.0%; MFI (230/5) 3.5 g/10 min; m.p. 153 0

C

Comparative Examples D F Polymerization was carried out analogously to Examples 4, 6 and 7 using the metallocene dimethylsilylbisindenylzirconium dichloride. The viscosity numbers and molecular weights of the resulting polymer products were: .".Comparative Polym. temp. VN M Example [cIm/gj [g/mol] D 70 47 37,500 E 50 60 56,000 F 30 77 76,900 Thbse Examples show the effect of the substituent in the 2-position on the indenyl ligand in respect of increasing the molecular weight.

Example 1 0 a A dry 16 dm 3 reactor was flushed with nitrogen. 40 dm 3 (corresponding to 2.5 bar) of hydrogen and finally 10 dm 3 of liquid propylene and 29.2 cm 3 of a solution of methylaluminoxane in toluene (corresponding to 40 mmol of Al, mean degree of oligomerization 17) were then metered in, and stirring was carried out at 30 0 C for 10 minutes.

At the same time, 2.7 mg (0.006 mmol) of rac-dimethylsilyl(2-Me-1-indenyl) 2 zirconium dichloride were dissolved 25 in 11.2 cm 3 of a solution of methylaluminoxane in toluene mmol) and introduced into the reactor after 10 minutes.

Polymerization was carried out for 3 hours after heating to 50 0 C. The polymerization was stopped by adding CO 2 gas, and excess gaseous monomer was alowed to escape. The metallocene activity was 102.9 kg of PP per g of metallocene per h.

VN 25 cm 3 M, 8,500 g/mol; M,/M 2.4; no olefinic chain ends according to 1 3 C-NMR; II 97.8%; m.p. 149°C Example 11 Example 10 was repeated, except that 5.0 mg (0.011 mmol) of rac-dimethylsilyl(2-Me-l-indenyl) 2 zirconiumdimethyl and 16 dm 3 (corresponding to 1 bar) of hydrogen were used.

Polymerization was carried out at 60°C for 50 minutes.

The metallocene activity was 204 kg of PP per g of metallocene per h.

VN 47 cm 3 M, 41,100 g/mol; 2.2; no olefinic chain ends according to "C-NMR; II 96.9%; m.p. 148°C Example 12 Example 11 was repeated with 4.2 mg (0.01 mmol) of rac- *e dimethylsilyl(2-Me-l-indenyl 2 zirconiumdimethyl. However, the polymerization temperature was 70°C and the polymerization time was 1 hour. The metallocene activity was 354 kg of PP per g of metallocene per h.

VN 38 cm 3 M 34,900 g/mol; M./Mn 2.1; no olefinic chain ends according to "C-NMR;- II 96.7%; m.p. 146°C Examples 10 to 12 show the good regulatability of the molecular weight with hydrogen when the polymerization process according to the invention was used.

26 Example 13 Example 11 was repeated, except that no hydrogen was used. The metallocene activity was 182.4 kg of PP per g of metallocene per h.

VN 210 cm 3

M

w 288,000 g/mol; M,/M n 2.2; II 96.2%.

Example 14 Example 11 was repeated, except that 4.2 mg (0.01 mmol) of rac-ethylene(2-Me-1-indenyl) 2 zirconiumdimethyl were used. The metallocene activity was 144.3 kg of PP per g of metallocene per h.

VN 16 cm 3 M, 8,900 g/mol; 2.0; II 96.0%.

0* Example A dry 24 dm 3 reactor was flushed with nitrogen and filled 15 with 12 dm 3 of liquid propylene and with 4.0 cm 3 of a solution of methylaluminoxane in toluene (corresponding to 6 mmol of Al, mean degree of oligomerization 17), and stirring was carried out at 30 0 C for 15 minutes. 2.5 cm 3 of the reaction mixture of rac-dimethylsilyl(2-Me-l- 20 indenyl)22zirconiumdimethyl and [Bu 3 NH] [B(C 6

H

5 which mixture was described in Section C) of the metallocene synthesis and corresponds to 17 mg (0.04 mmol) of metallocene, in toluene, were metered into the vessel.

Polymerization was carried out at 50 0 C for 1 hour. The metallocene activity was 61.4 kg of PP per g of metallocene per h.

VN 238 cm 3 M, 328,500 g/mol; M,/Mn 2.2; II 96.0%.

27 Example 16 Example 15 was repeated, except that 2.5 cm 3 of the reaction mixture of rac-ethylene(2-methyl-l-indenyl)2zirconiumdimethyl and [Bu 3 NH][B(p-tolyl)J], which mixture was described in Section F) of the metallocene synthesis and corresponds to 16.3 mg (0.04 mmol) of metallocene, in toluene, were used. The metallocene activity was 42.9 kg of PP per g of metallocene per h.

VN 105 cm 3

M

w 110,500 g/mol; M,/M 2.3; II 96.0%.

Example 17 Example 15 was repeated, except that a solution of trimethylaluminum in toluene (8 mmol of Al) was used instead of the methylaluminoxane solution. The metallocene 15 activity was 55.3 kg of PP per g of metallocene per h.

VN 264 cm3/g; M, 367,000 g/mol; 2.3; II "96.2%.

Example 18 Example 17 was repeated, except that no trimethylaluminum was used in the polymerization.

The propylene used was purified with triethylaluminum (1 mmol of AlEt 3 /dm 3 of propylene) before being added to the polymerization system, and the reaction products and AlEt 3 were separated off by distillation. The metallocene :25 activity was 56.9 kg of PP per g of metallocene per h.

4 VN 278 cm 3 M, 362,000 g/mol; M./M4 2.3; II 96.3%.

28 Example 19 A dry 16 dm 3 reactor was flushed with nitrogen and filled at 20°C with 10 dm 3 of a gasoline cut from which aromatics had been removed and which had a boiling range of 100 120 0

C.

The gas space of the vessel was then flushed nitrogen-free by forcing in 2 bar of ethylene and letting down the pressure, these operations being carried out 5 times.

Thereafter, 30 cm 3 of a solution of methylaluminoxane in toluene (corresponding to 45 mmol of Al, molecular weight according to cryoscopic determination 750 g/mol) were added.

The reactor content was heated to 60°C in the course of 15 minutes while stirring, and the total pressure was .15 adjusted to 5 bar at a stirring speed of 250 rpm by 0** adding ethylene.

*O

At the same time, 2.3 mg (0.005 mmol) of rac-ethylene(2methyl-l-indenyl)zzirconium dichloride were dissolved in cm 3 of a solution of methylaluminoxane in toluene and preactivated by allowing the solution to stand for minutes. The solution was then introduced into the reactor, and the polymerization syosem was brought to a temperature of 70°C and kept at this temperature for 1 hour by appropriate cooling. The total pressure was kept 5 at 5 bar during this time by appropriate supply of ethylene.

420 g of polyethylene were obtained, corresponding to a metallocene activity of 182.6 kg of PE per g of metallocene per h. The viscosity number was 300 cm 3 /g.

Comparative Example G Polymerization was carried out with the metallocene 29 rac-ethylene (-indenyl) zirconium dichloride under conditions analogous to Example 19. A polyethylene having a viscosity number of 210 cm 3 /g was obtained.

The Comparative Example demonstrates the effect of substitution in the 2-position of the indenyl ligand in respect of increasing the molecular weight.

Example Example 7 was repeated, except that the aluminoxane used was isobutylmethylaluminoxane in the same Al concentration and amount. The metallocene activity was 27.4 kg of PP per g of metallocene per h, M, was 477,500 g/mol, tha VN was 340 cm 3 /g an M,/Mn was 2.2. Isobutylmethylaluminoxane was obtained by reacting a mixture of isobutyl-AlMe 2 and AlMe 3 with water in heptane and contained 15 9 mol of isobutyl units and 91 mol of methyl units.

Example 21 Example 7 was repeated, except that the aluminoxane used was hydridomethylaluminoxane (prepared from MeAlH and water in toluene) in the same Al concentration and amount. The activity was 22.9 kg of PP per g of metallocene per h, M, was 469,500 g/mol, the VN was 339 cm3/g and was Example 22 A dry 150 dm 3 reactor was flushed with nitrogen and 25 filled, at 20 0 C, with 80 dm 3 of a gasoline cut from which aromatics had been removed and which had a boiling range of 100 120 0 C. Thereafter, the gas space was flushed nitrogen-free by forcing in 2 bar of propylene and letting down the pressure, these operations being carried out 5 times.

After the addition of 50 1 of liquid propylene, 64 cm 3 of 30 a solution of methylaluminoxane in toluene (corresponding to 100 mmol of Al, molecular weight according to -ryoscopic determination 990 g/mol) were added and the reactor content was heated to 30 0

C.

By metering in hydrogen, a hydrogen content in the gas space of the reactor of 0.3% was established and was subsequently maintained during the entire polymerization time by further metering (on-line monitoring by gas chromatography).

24.3mg of rac-dimethylsilyl(2-methyl-l-indenyl) zirconium dichloride (0.05 mmol) were dissolved in 32 ml of a solution of methylaluminoxane in toluene (corresponding to mmol of Al), and the solution was introduced into the reactor after 15 minutes.

15 The reactor was kept at the polymerization temperature of 30 0 C for 24 hours by cooling, and the polymerization was then stopped by adding 2 bar of CO 2 gas and the polymer a formed was isolated from the suspension medium over a pressure filter. The product was dried for 24 hours at 800/200 mbar. 10.5 kg of polymer powder, corresponding to a metallocene activity of 18.0 kg of PP per g of metallocene per h, were obtained.

VN 256 cm 3 340,500 g/mol; 2.2; II 97.3%; MFI (230/5) 5.5 g/10 min; m.p. 156°C Example 23

S

Example 22 was repeated, except that 0.6% of H2 was established in the gas space, .20.6 mg (0.043 mmol) of the metallocene were used and the polymerization temperature was 50 0

C.

19.2 kg of polymer powder, corresponding to a metallocene activity of 38.8 kg of PP per g of metallocene per h, were obtained.

31 VN 149 cm 3 M, 187,500 g/mol; 2.3; II 97.0%; MFI (230/5) 82 g/10 min; m.p. 150°C Example 24 Example 23 was repeated, except that no hydrogen was used, the weight of metallocene was 31.0 mg (0.065 mmol) and the polymerization time was 4 hours.

kg of polymer powder, corresponding to a metallocene activity of 64.5 kg of PP per g of metallocene per h, were obtained.

VN 175 cm 3 M, 229,000 g/mol; M,/Mn 2.2; II 97.1%; MFI (230/5) 35 g/10 min; m.p. 150 0

C

Example Example 1 was repeated, except that 4.1 mg (0.008 mmol) of the metallocene rac-phenyl (methyl) silyl (2-methyl-lindenyl) 2 ZrCl 2 were used.

1.10 kg of polypropylene were obtained, corresponding to an activity of the metallocene of 269 kg of PP per g of metallocene per h.

VN 202 cm 3 M, 230,000 g/mol; M /Mn 2.3; II 97%; 20 MFI (230/5) 36 g/10 min; m.p. 147°C Example 26 Example 25 was repeated with 11.0 mg (0.02 mmol) oi the metallocene, but the polymerization temperature was

S

1.05 kg of polypropylene were obtained. The activity of the metallocene was 95.5 kg of PP per g of metallocene per h.

VN 347 cm 3 444,000 g/mol; M./Mn 2.5; MFI 32 (230/5) 5.2 g/10 min; m.p. 149'C Example 27 Example 25 was repeated with 22.5 mg (0.04 nimol) of the metallocene, but the polymerization temperature was 0.57 kg of polypropylene was obtained and the activity of the metallocene was thus 25.3 kg of PP per g of metallocene per h.

Ir 494 cm 3 666,000 q7/mol; 2.5; MFI (230/5) 1.3 g/10 min; m.p. 152 0

C

Example 28 Example 1 was repeated, except that 5.2 mig (0.009 mmol) of the metallocene rac-diphenylsilyl(2-methyl-1indenyl) 2 ZrCl., were used.

000 L14 kg of polypropyLene were obtained. The metallocene 15~l activity was thus 2319 kg of PP per g of metallocene per h.

VN 298 cm 3 367,000 g/mol; 2.2; MFI (230/5) 7.1 g/10 min Example 29 Example 28 was repeated with 12.6 mig (0.02 nimol) of the 0:2 0 metallocene but the polymerization temperature was 40 0

C.

0. 44 kg of polypropylene was obtained and the metallocene activity was thus 34.9 kg of PP per g of metallocene per h.

S VN 646 cm 3 845,000 g/mol; M,,/Mn 2.4; MFI (230/5) 0.1 g/10 min; m.p. 155 0

C

33 Example Example 1 was repeated, except that 17.4 mg (0.038 mmol) of the wetallocene rac-methylethylene(2-methyl-1indenyl) ZrCl 2 were used.

2.89 kg of polypropylene were obtained. The metallocene activity was thus 165.9 kg of PP per g of metallocene per h.

VN 138 cm 3 M, 129,000 g/mol; ,/Mn 2.2; m.p. 150°C Example 31 Example 30 was repeated with 15.6 mg (0.034 mmol) of the metallocene but the polymerization temperature was 50 0

C

and the polymerization time was 2 hours.

2.86 kg of polypropylene were obtained. The metallocene 15 activity was thus 91.7 kg of PP per g of metallocene per h.

v x r 244 cm 3 M 243,500 g/mol; M/M, 2.1; m.p. 155 0

C

Example 32

S

Example 30 was repeated with 50.8 mg (0.110 mmol) of the metallocene but the polymerization temperature was 30 0

C.

1.78 kg of polypropylene were obtained and the metallocene activity was thus 17.5 kg of PP per g of metallocene per h.

VN 409 cmr 3 M, 402,000 g/mol; 2.2; MFI (230/5) 3.5 g/10 min; m.p. 160°C 34 Example 33 Example 1 was repeated, except that 9.6 mg (0.02 mmol) of the metal locene rac -diznethyls ilyl (2 -methyl-1I-indenyl) 2 zirconium dichloride were used.

1.68 kg of polypropylene, corresponding to a metallocene activity of 175.0 kg of PP per g of metallocene per h were obtained.

VN 143 CM3/g; M, 132,000 g/mol; 2.3; m-p.

140 0

C

Example 34 Example 33 was repeated, except that 10.4 mg (0.021 nimol) of the nietallocene were Used and the polymerization temperature was 50 0

C.

08 0 1.00 kg of polypropylene, corresponding to a metallocene activity of 96.2 kg of PP per g of metallocene per h, a were obtained.

=303 cm 3 449,300 g/mol; 2.2; m.p.= 145 0

C

Example 0:.20 Example 33 was repeated with 24.5 mig (0.049 nimol) of the metallocene at a polymerization temperature of 30 0

C.

0.49 kg of polypropylene, corresponding to a metallocene activty of 19.6 kg of PP per g of metallocene per h, was obtained.

VV 442 cm 3 M~=564,000 g/mol; MW/M. 2.2; m.p.

150 0

C

35 Example 36 A dry 24 din 3 reactor was flushed with nitrogen and filled with 2.4 din 3 of hydrogen and 12 din 3 of liquid propylene.

35 cm 3 of a solution of methylaluininoxane in toluene (corresponding to 52 znmol of Al, mean degree of oligomerization p 17) were then added.

At the same time, 8.5 mg (0.02 mmol) of rac-diinethylsilyl (2-methyl-1-indenyl 2 zirconiun dichlori,-e were dissolved in 13.5 cm 3 of a solution of methyJlaluininoxane i~a toluene (20 mmo. of Al) and preactivated by allowing the solution to stand for 5 minutes.

The solution was thea introduced into the reactor.

Polymerization was carried out for 1 hour at 55 0 C writh continuous addition of 50 g of ethylene.

*O.The metallocene activity was 134 kg of C 2

/C

3 -copolymer per g of metallocene per h.

The ethylene content of the copolymer was 4.3%.

VIN 289 ';M 3 402,000 g/mol; 2.0; MFI j230/5) 7A0 g/10 min The~ ethylene was substantially incorporated as isolated units (1 3 C-NMR, mean block leagth C 2 4 1.2).

4 Example 31;' "Soo A dry 150 din 3 reactor was prepared as described in Example 22 and charged with propylene and catalyst.

The polymerization was carried out in a first stage at 0 C for 10 hours.

r 36 In a second stage, 1 kg of ethylene was first rapidly added and a further 2 kg of ethylene were metered in continuously in the course of 4 hours.

21.5 kg of block copolymer powder were obtained.

VN 326 cm 3 M 407,000 g/mol; M,/M n 3.1; MFI (230/5) 4.9 g/10 miin The block copolymer contained 12.5% of ethylene.

Fractionation gave a content of 24% of ethylene/propylene rubber in the copolymer. The mechanical data of the copolymer were: Ball indentation hardness (DIN 53,456, pressed sheets, heated at 140°C for 3 h, 132 N) 60 Nmm 2 notched impact strength injection molded specimens according to DIN 53,453) 23 0 C: no fracture, 0 C: 39.5 mJmm 2 -40 0 C: 20.1 mJmm" 2 The product is distinguished by an exceptional hardness/ impact strength relationship and can be used for structural components, for example in automotive construction bumpers), where high rigidity coupled with high impact strength, in particular at low temperatures, is required.

Abbreviations: Me Methyl, Et Ethyl, Bu Butyl, Ph Phenyl, THF Tetrahydrofuran, PE Polyethylene, PP Polypropylene.

Claims

1. A process for the preparation of an olefin polymer by polymerization or copolymerization of an olefin of the formula Ra-CH=CH-R b wherein R a and Rb are identical or different and are a hydrogen atom or a hydrocarbon radical having 1 to 14 C atoms, or Ra and Rb, together with the atoms binding them, may form a ring, at a temperature of -60 to 200 0 C, at a pressure of 0.5 to 100 bar, in solution, in suspension or in the gas phase, in the presence of a catalyst which is composed of a metallocene as the transition metal compound and an aluminoxane of the formula (II) R 1 4 R 1 R1 R -14 Al 0 A Al (II) R 1 4 R14 for the linear type or of the formula (III) a o R14 I 15P2 (III) for the cyclic type, wherein, in the formulae (II) and (III), the radicals R 14 may be identical or different and are a Ci-C6-alkyl group, a C-C 1 -aryl group or hydrogen, and p is an integer of :20 from 2 to bO, wherein the metallocene is a compound of the formula I 1* 0 8 9 (CR R) R* "M 6 R7 T1 1 R I b2> 1 R 6 n (I) 38 wherein MI is a metal of group IVb, Vb or VIb of the Periodic Table, R' and R 2 are identical or different and are a hydrogen atom, a C,-C 1 -alkyl group, a C 1 -C 1 -alkoxy group, a Cr 6 -Cl-aryl group~, a C-C-aryloxy group, a -C- alkenyl group, a C 7 -C 40 -arylalkyl group, a C 7 -C4 0 alkylaryl group, a C.-C 4 -arylalkenyl group or a halogen atom, R 3 and R 4 are identical or different and are a hydrogen atom, a halogen atom, a C,-C,,-alkyl group which may be halogenated, a Cr,-C 1 -aryi. group, an -NR 2 10 -SR' 0 -OSi- R 3 10 I -SiR 3 1 0 or -PR 2 10 radical, wherein R10 is a halogen atom, a C,,-Cl.-alkyl group or a C 5 -Cl-aryl group, R 5 and R 6 are identical or different and have the meaning stated for R 3 and R with the proviso that R 5 and R 6 are not hydrogen, R 7 is R1 R 1 1 Ril R 1 1 R 1 1 I I M (CR 13 -M 0 i. 12 112 R R 9 =BR' 1 =AlR1 1 =SO, =S021 =NR 11 =CO, 20 =PR" or P)RL wherein R 11 R1 2 and R 1 3 ar. Ldentical or different and are a hydrogen atom, a halogen atom, a C 1 -Cl-alkyl group, I oo 4 39 a C,-C.-fluoroalkyl group, a C 6 -C 1 0 -aryl group, a C 8 ,-C 1 -fluoroaryl group, a C 1 -C 1 -alkoxy group, a C 2 -Cl-alkenyl group, a C 7 -C 40 -arylalkyl group, a C 8 -C 4 0 -arylalkenyl group or a C--C 4 -alkylaryl group, or R" 1 and R 1 2 or R' 1 and R" 3 together with the atoms binding them, each form a ring, M2 is siiogermanium ortin, R,8 and R 9 are identical or different and have the meaning stated for and m and n are identical or different and are zero, 1 or 2, m plus n being zero, 1 or 2.

2. The process claimed in cla .a 1, wherein, inthe formula 1, M4 1 is Zr or Hf, R1 and R 2 are identical or P *different and are methyl or chlorine, R 3 and R 4 are 1 hydrogen, R 5 and R6 are identical or different and are methyl, ethyl or trifluoromethyl, R 7 is a radical 0- bo 1 R 1 1 112 R4 R and n plus m is zero or 1.

3. The process as claimed in claim 1 or 2, wherein the compound of the formula I is rac-dimethylsilyl(2-methyl- :0 20 1-indenyl zirco,iiumfdichioride, rac -ethylene (2 -methyl-il- indenyl )7azirconium dichloride, rac-dimethylsilyl (2-methyl- 1-indenyl 2 zircont-mdi~methyl, rac-ethylene (2-methyl-i- indenyl 2 ziLrconiumdimethyl, rac-phenyl (methyl) silyl (2- methyl-l-indenyl) 2 Zirconium dichloride, rac-diphenyl- silyl(2-methyl-l-indenyl) 2 Zirconium dichloride, rac- methylethylene (2-methyl-1-indenyl) 2 Zirconium dichloride or rac -dimethyls ilyl1 (2 -ethyl -1-indenyl 2 Z irconium dichloride. in one or moeo las a catalyst in the ^riaato f an eief-ii--Pev- An olef in polymer which can be prepared by the process as claimed in one or more of claims 1 to 3. DATED this 8th day of November 1991. HOECHST AKTIENGESELLSCHAFT WATERMARK PATENT TRADEMARK ATTORNEYS "THE ATRIUM" 290 BURWOOD ROAD HAWTHORN. VIC. 3122. oat**0 0 *000 *so* *000 00 *0 se* 0 0 *$Ato: 00*4 HOE 90/F 334 Abstract of the Disclosure Process for the preparation of a high molecular weight olefin polymer A very active catalyst system for olefin polymerization is composed of an aluminoxane and a metallocene of the formula I 89 (CR R) k *i i SR* MR 1 7 p M 6 R R I 4t S R R C Rn wherein preferably M 1 is Zr or Hf, R 1 and R 2 are alkyl or halogen, R 3 and R 4 are hydrogen, R 5 and R 6 are alkyl or *t haloalkyl, -(CR 8 9 is a single-membered or multimembered chain in which R 7 may also be a (sub- stituted) hetero atom, and m+n is zero or 1. The catal- yst system gives polymers having a high molecular weight and high stereospecificity.