CA2350563A1

CA2350563A1 - Method for producing an ep(d)m with bridged pentadienyl-fluorenyl transition metal complex

Info

Publication number: CA2350563A1
Application number: CA002350563A
Authority: CA
Inventors: Rudiger Engehausen; Wolfgang Nentwig; Peter Schertl; Walter Kaminsky; Ulrich Weingarten; Ralf Werner
Original assignee: Individual
Current assignee: Bayer AG
Priority date: 1998-11-05
Filing date: 1999-10-25
Publication date: 2000-05-18
Also published as: JP2002529555A; AU1265900A; WO2000027894A1; DE19850898A1; EP1149120A1

Abstract

The invention relates to a method for producing rubber-type ethylene-propylene copolymers and ethylene-propylene non-conjugated diene terpolymers and to the use of the polymers obtained by said method for producing shaped bodies of any kind.

Description

PROCESS FOR THE PREPARATION OF EP(D)M WITH A BRIDGED
PENTADIENYL-FLUORENYL TRANSITION METAL COMPLEX
The present invention relates to a process for the preparation of rubber-like ethylene/propylene copolymers and ethylene/propylene/non-conjugated dime terpolymers, and to the use of the polymers obtainable in this way for the production of all types of shaped articles.
Because of their saturated main chain, ethylene/propylene copolymers (EPM) and ethylene/propylene/non-conjugated dime terpolymers (EPDM) are important starting substances in industry. To obtain their final properties, the polymers must be crosslinked with peroxides, radiation or sulfur/sulfur agents. The content of unsaturated bonds in EPDM, which is adjusted via the content of non-conjugated dime, is of importance precisely in the case of sulfur crosslinking. Many catalysts have been developed for tailor-making the composition and microstructure of EPM
and EPDM.
It is prior art to prepare EPM and EPDM with catalysts based on Ziegler-Natta systems. Vanadium-containing catalysts are usually employed for this. The processes are carried out in solution, suspension or the gas phase.
It is prior art to prepare ethylene/propylene copolymers with bis-cyclopentadienyl-zirconium compounds (EP-B-129 368), but the degree of incorporation of non-conjugated dime is usually unsatisfactory.
US-A-4.892.851 discloses a compound in which a cyclopentadienyl ligand (cp) is linked with a fluorenyl ligand (flu) via a dimethylmethylene bridge.
The doctrine of EP-A2-512 554 is also bridged cp-flu compounds and the use thereof as catalysts for the polymerization of olefins.
~7 33 36~

The doctrine of US-A-x.158.920 is bridged cp-flu compounds and the use thereof for the preparation of stereo-specific polymers. Bridged cp-flu compounds are also known from further documents, but all the documents have the common feature that the bridge member is a linear chain. However. the catalysts of this type show weaknesses in the chain length of the EP(D)M obtained, so that oils or waxes, which cannot be used for the production of shaped articles. are often obtained.
There was thus the object of providing a process for the preparation of EPM
and EPDM which does not have the disadvantages of the prior art.
This object is achieved according to the invention by a process for the polymerization of ethylene, propylene and optionally a non-conjugated dime employing a metallocene as the catalyst. characterized in that the metallocene employed is a compound of the general formula (I) IJ
Ra R: LRs R
R"
M ,.."... X
20 R3 R\ ~X (I)~

R ~ w~w~R
w ~ \ Rs ~~ w w R'3.-w~ ~R,o ~w w ~ ~ R"
25 R'2 wherein R' to R~' independently of one another represent H. C,-Ci2-alkyl, C~-C,Z-aryl or C~-C,Z-aralkyl radicals, X represents H, halogen or C,-C,z-alkyl radicals, W represents a carbon atom or an optionally substituted atom of groups 13, 1 S
or 16, Y represents C,-C,2-alkyl radicals or an optionally substituted atom of groups 14, 15 or 16 and M represents a metal of group 4, optionally in the presence of one or more co-catalysts.
C,-C,2-Alkyl is understood as meaning all the linear or branched alkyl radicals having 1 to 12 C atoms known to the expert, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, neo-pentyl and hexyl, which in their turn can again be substituted. Possible substituents here are halogen or also C,-C,2-alkyl or -alkoxy, as well as C6 C,2-cycloalkyl or -aryl, such as benzoyl, trimethylphenyl, ethylphenyl, chloromethyl and chloroethyl.
C,-C,2-Alkoxy is understood as meaning all the linear or branched alkoxy radicals having 1 to 12 C atoms known to the expert, such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, t-butoxy, n-pentoxy, i-pentoxy, neo-pentoxy and hexoxy, which in their turn can again be substituted. Possible substituents here are halogen or also C,-C,2 alkyl or -alkoxy, as well as C6 C,2-cycloalkyl or -aryl.
C6 C,2-Aryl is understood as meaning all the mono- or polynuclear aryl radicals having 6 to 12 C atoms known to the expert, such as phenyl and naphthyl, which in their turn can again be substituted. Possible substituents here are halogen, nitro, hydroxyl or also C,-C,Z-alkyl or -alkoxy, as well as C6 C,Z-cycloalkyl or -aryl, such as bromophenyl, chlorophenyl, toluyl and nitrophenyl.

C,-C,2-Aralkyl is understood as meaning a combination of the above alkyls with the abovementioned aryls.
The radicals R' to R'z are preferably hydrogen, methyl, ethyl, propyl, t-butyl, methoxy, ethoxy, cyclohexyl, benzoyl, methoxy, ethoxy, phenyl, naphthyl, chlorophenyl and toluyl.
If the radicals X represent halogen, this is understood by the expert as meaning fluorine, chlorine, bromine or iodine, and chlorine is preferred.
If Y represents an atom of groups 14, 1 S or 16, this is understood as meaning preferably Si, Ge, Su, Pb, N, P, O and S. Si, N and P are particularly preferred.
M represents Ti, Zr and Hf, and Zr is preferred.
Catalysts of the general formula (II) R' R~ c~
R 5«"","
R°
R (II) 3 R' M~' Rrs \\ Rs a ~~ R
~''L R,~ R:
wherein R' to R'Z independently of one another represent H, C,-C,Z alkyl or C6 C,2-aryl radicals, ' WO 00/27894 PCT/EP99/08064 X represents Cl or methyl and M represents Ti or Zr are preferably employed.
The catalyst of the formula (III) """", a Zr .",~" CI
(EI)~
~ CI
is very particularly preferably employed.
The invention also provides the compounds of the formula (I), (II) and (III).
The compounds of the formula (I), (II) and (III) are often employed in combination with co-catalysts for the polymerization according to the invention. Possible co-catalysts are the co-catalysts known in the field of metallocenes, such as polymeric or oligomeric alumoxanes, Lewis acids and aluminates and borates. In this connection reference is made in particular to Macromol. Symp. vol. 97, July 1995, p. 1 - 246 (for alumoxanes) and to EP 277 003, EP 277 004, Organometallics 1997, 16, 842-857 (for borates) and EP 573 403 (for aluminates). Particularly suitable co-catalysts are methylalumoxane, methylalumoxane modified by triisobutylaluminium (TIBA) and diisobutylalumoxane, trialkylaluminium compounds, such as trimethylaluminium, triethylaluminium, triisobutylaluminium and triisooctylaluminium, and moreover dialkyaluminium compounds, such as 'WO 00/27894 PCT/EP99/08064 diisobutylaluminium hydride and diethylaluminium chloride, substituted triarylboron compounds, such as tris(pentafluorophenyl)borane, and ionic compounds which contain tetrakis(pentafluorophenyl)borate as the anion, such as triphenylmethyl tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis(pentafluorophenyl)borate and N,N-dimethylanilinium tetrakis (pentafluorophenyl)borate, substituted triaryaluminium compounds, such as tris(pentafluorophenyl)aluminium, and ionic compounds which contain tetrakis(pentafluorophenyl)aluminate as the anion, such as triphenylmethyl tetrakis(pentafluorophenyl)aluminate and N,N-dimethylanilinium tetrakis (pentafluorophenyl)aluminate.
It is of course possible to employ the co-catalysts as a mixture with one another.
The most favourable mixture ratios in each case can be determined by suitable preliminary experiments.
The polymerization according to the invention is carried out in the gas, liquid or slurry (suspension) phase. The temperature range for this extends from -20°C to +200°C, preferably 0°C to 160°C, particularly preferably +20°C to +80°C; the pressure range extends from 1 to 50 bar, preferably 3 to 30 bar.
Polymerization-inert solvents which are co-used are, for example: saturated aliphatics or (halogeno)aromatics, such as pentane, hexane, heptane, cyclohexane, petroleum ether, petroleum, hydrogenated benzines, benzene, toluene, xylene, ethylbenzene, chlorobenzene and analogues or mixtures thereof. These reaction conditions for the polymerization are known in principle to the expert.
The polymerization according to the invention is preferably carried out in the presence of inert organic solvents. Possible inert organic solvents are, for example:
aromatic, aliphatic and/or cycloaliphatic hydrocarbons, such as, preferably, benzene, toluene, hexane, pentane, heptane and/or cyclohexane or mixtures thereof. The polymerization is preferably conducted as solution polymerization or in suspension.

' WO 00/27894 PCT/EP99/08064 In another preferred embodiment the process according to the invention is carried out in the gas phase. The polymerization of olefins in the gas phase was realized technologically for the first time in 1962 (US 3.023.203). Corresponding fluidized bed reactors have been prior art for a long time.
The organometallic compound of the formula (I), (II) or (III) and optionally the co-catalyst are also applied to an inorganic support and employed in heterogenized form when used in suspension or the gas phase. Suitable inert inorganic solids are, in particular, silica gels, clays, alumosilicates, talc, zeolites, carbon black, inorganic oxides, such as silicon dioxide, aluminium oxide, magnesium oxide or titanium dioxide, or silicon carbide, preferably silica gels, zeolites and carbon black. The inert inorganic solids mentioned can be employed individually or as a mixture with one another. In another preferred embodiment organic supports are employed individually or as a mixture with one another or with inorganic supports.
Examples of organic supports are porous polystyrene, porous polypropylene or porous polyethylene.
Possible non-conjugated dimes are all the dimes known to the expert in which the double bonds have different reactivities towards the catalyst system employed, such as 5-ethylidene-2-norbornene (END), 5-vinylnorbornene, 1,4-hexadiene, 7-methyl-1,6-octadiene and dicyclopentadiene. 5-Ethylidene-2-norbornene and 1,4-hexadiene are preferred.
It may be advantageous to purify the starting substances to remove impurities, such as oxygen, water or polar substances. The polymerization is in general conducted under inert conditions.
The rubber-like EPM and EPDM which can be prepared according to the invention are distinguished by a low crystalline content. The crystalline content is in general less than 30%, preferably less than 20%, particularly preferably less than 10%, very _g_ particularly preferably in the range from 0 to 10%. The crystalline content can be determined by measurements of the fusion enthalpy ratios and by the DSC
method.
The following factor has proved appropriate here:
crystallinity - fusion enthalpy J/g B100 J/g The non-crosslinked EPM and EPDM are readily soluble in the usual solvents, such as hexane. heptane or toluene.
1 () The ethylene content is in the range from 5 to 95 wt.%. preferably 40 to 90 wt.%.
The propylene content is in the range from ~ to 95 wt.%, preferably 9.5 to X9.5 wt.%.
1 ~ The content of non-conjugated dime is in the range from 0 to 20 wt.%.
preferably 0.5 to 12 wt.%.
It is commonplace that the individual contents of the monomers must add up to 100% and an expert will accordingly choose them appropriately from the individual w-t.% ranges.
It is a particular advantage of the process according to the invention that the catalyst can remain in the end product and causes no interference during further processing or use.

The further processing of the EPM and EPDM which can be prepared according to the invention usually comprises a crosslinking step with peroxides.
sulfur/sulfur donors or high-energy radiation. This step is known to the expert. but reference may be made expressly at this point to "Handbuch fiir die Gummi-Industrie, published by Bayer AG, Leverkusen, 2nd edition. 1991; p. 231 et seq.". The EPM and EPDM can also be extended with oils, if this is desired.
The invention also provides the use of the rubber-like EPM and EPDM which can be prepared according to the invention for the production of all types of shaped articles.
Shaped articles which may be mentioned are seals, O-rings, profiles, sheets, coverings for other materials and damping elements.
For applications in the low temperature range. it may be advantageous to employ 1 (> products with a crystallinity in the range from 0 to 5%.
It is of course possible also to employ the rubber-like EPM and EPDM according to the invention as a mixture with other polymers or rubbers, such as SBR, BR, CR, NBR; ABS. HNBR. polyethylene, polypropylene, polyethylene copolymers, LDPE, I ~ LLDPE, HDPE. HMWPE, polysiloxanes, silicone rubbers and fluorinated rubbers.
Corresponding mixtures are known to the expert and can be optimized by a few experiments.
It may also be advantageous to add fillers, such as carbon black. silica, talc, silicic ?0 acids and metal oxides. These fillers and their use are known to the expert, but reference may be made expressly to the Encyclopaedia of Polymer Science and Engineering, vol. 4, p. 66 et seq.

Examples All work up to the working up of the polymer was carned out in an inert gas atmosphere using Schlenk, spraying and glovebox techniques. Argon from Linde with a purity of >_99.996%, which was after-purified by means of an Oxisorb cartridge from Messer-Griesheim, DE, was used as the inert gas. The toluene used for polymerizations and for preparation of catalyst and co-catalyst stock solutions was obtained from Riedel-de-Haen, DE, with a purity of >_99.5%. It was predried over potassium hydroxide for several days, degassed, heated under reflux over a sodium/potassium alloy for at least one week and finally distilled for use.
Example 1: Preparation of 1,3,3-trimethyl-2,3-dihydropentalene 600 ml methanol, 50 ml (0.61 mol) freshly distilled cyclopentadiene and 75 ml (0.61 mol) diacetone alcohol are placed under argon in a 1 1 NZ flask. After controlling the temperature of the mixture to 0°C, 80 ml freshly distilled pyrrolidine are added. After warming to room temperature the mixture is stirred for 18 hours.
The intensely yellow-coloured solution is concentrated to 200 ml and distilled over a 30 cm Vigreux column. 16.9 g of a yellow-orange, viscous oil (distillation temperature 64 to 70°C) are isolated under an oil pump vacuum at an oil bath temperature of 130 to 160°C. This fraction is distilled over a mirrored 25 cm cracking tube column. 2.1 g (14 mmol) of the desired product are obtained under 11 mbar at a distillation temperature of 66 to 69°C and at an oil bath temperature of 150°C. The 'H-NMR spectrum shows a product to 6,6-dimethylfulvene ratio of 5 to 1.
'H-NMR (100 MHz, CDC13, J [Hz], TMS):
8 [ppm]: 6.72 (1 H, d, 3J = 5.0, olefin. Cp proton) 6.06 (2 H, dd,'J = 5.0, 4J = 0.8, olefin. Cp protons) 2.82 (2 H, s, methylene protons) ' WO 00127894 PCT/EP99/08064 2.14 (3 H, s, methyl protons) 1.26 (6 H, s, methyl protons) Example 2: Preparation of 1-fluorenyl-1,3,3-trimethyl-1,2,3,6-tetrahydropentalene 9.56 ml (15.3 mmol) of a 1.6 N solution of n-butyllithium in hexane are added dropwise to a mixture of 2.54 g (15.3 mmol) fluorene in 50 ml THF in a 250 ml Nz flask with a dropping funnel and reflux condenser at -50°C in the course of 30 minutes. A$er warming to room temperature the solution is stirred for a further eight hours and then heated briefly at the boiling point. After cooling to -50°C
1.68 g (11.5 mmol) 1,3,3-trimethyl-2,3-dihydropentalene in 20 ml THF are added dropwise in the course of two hours and the mixture is stirred overnight at room temperature. After boiling up briefly, 20 ml half concentrated hydrochloride acid are added. The low aqueous phase is saturated with NaCI and extracted with diethyl ether. The combined organic phases are washed twice with 20 ml saturated NaCI
solution each time. They are then dried over NazS04. After all the solvent has been condensed off in a rotary evaporator, 5.0 g of crude product are obtained as an orange-yellow, viscous oil. The ligand is purified by column chromatography (silica gel 60; particle size 0.015-0.040 mm; petroleum ether 60/70). Yield: 1.10 g (3.5 mmol; 30%, based on the pentalene) 'H-NMR (100 MHz, CDCI3, TMS):
8 [ppm]: 7.83-6.97 (8 H, m, arom. protons) 6.65-6.32 (2 H, m, olefin. Cp proton) 4.05 (1 H, s, aliph. fluorene proton) 3.40, 3.02, 2.72 (2 H, m, aliph. Cp protons) 1.73. 1.69 (3 H, s, methyl protons, 2 isomers) 1.34-1.18 (2 H, m, methylene protons) 0.98 (3 H, s, methyl protons) 0.30 (3 H, s, methyl protons) WO 00/27894 PCT/EP99/080br4 Mass spectrum: m/z 312 (molecular peak) Example 3: Preparation of [1-(rls-fluorenyl)-1,3,3-trimethyl-rls-tetrahydro-pentalenyl]-zirconium dichloride 4.4 ml (8.0 mmol) of a 1.8 molar solution of n-butyllithium in hexane are added dropwise to a mixture of 1.1 g (3.2 mmol) 1-fluorenyl-1,3,3-trimethyl-1,2,3,6-tetrahydropentalene in 25 ml THF at room temperature. After four days the mixture is heated briefly at the boiling point. After complete condensation of the solvent the precipitate formed is washed twice with 10 ml pentane each time. After decanting the pentane 0.75 g (3.2 mmol) zirconium tetrachloride and, at -60°C, 35 ml pentane are added. The mixture is stirred at room temperature for three and a half days.
After decanting the pentane the residue is extracted with a total of 60 ml methylene chloride. After concentrating the solution 1.94 g of crude product are obtained.
After renewed recrystallization from methylene chloride 150 mg (0.3 mmol, 10%
based on the zirconium tetrachloride) of the product are obtained as a crystalline, red, photosensitive solid. (X-ray structural analysis: fig. 3) Mass spectrum: m/z 472 (molecular peak) Polymerization:
Methylaluminoxane from Witco was used as the co-catalyst. This was employed as a solution in toluene with a concentration of 100 mg/ml.
The gaseous monomers ethene (Linde) and propene (Gerling, Holz & Co.) used have parities of >_99.8%. Before introduction into the reactor they were passed through two purification columns in each case in order to remove traces of oxygen and sulfur. The two columns had dimensions of 3 ~ 300 cm3, an operating pressure of 8.5 bar and an operating temperature of 25°C and ensured a volume flow of approx.

~WO 00/27894 PCT/EP99/08064 1/min. 'The first column in each case was filled with Cu catalyst (BASF R3-11) and the second in each case with a molecular sieve ( 10 ~).
The 5-ethylidene-2-norbornene (ENB) was obtained as a mixture of the endo and 5 exo form with a purity of >_99% from Aldrich, degassed, stirred with n-tributylaluminium (Witco, 20 ml per 1 1 ENB) for one week and condensed off.
Procedure The apparatus was first tested for leaks, during which both a vacuum applied and an 10 argon pressure introduced of 4 bar had to remain constant for several minutes. Only.
then was the apparatus heated thoroughly for one hour at 95°C under an oil pump vacuum. The reactor was then brought to the reaction temperature of 30 or 60°C and charged. The temperature was maintained with an accuracy of ~ 1 °C
during the reaction.
For the terpolymerizations 500 ml toluene and 10 ml MAO solution were initially introduced in counter-current with argon and the particular amount of the liquid monomer (ENB) required was then added. The solution was saturated first with propene and then with ethene. When saturation was reached, the polymerization was started by spraying in the metallocene solution. The ethene was topped up during the reaction so that the overall pressure remained constant during the reaction, but the monomer composition of the batch changed constantly. The reactions were therefore interrupted at low conversions. The reaction was ended by destroying the catalyst by spraying in 5 ml ethanol and the gaseous monomers were let down carefully in a fume cupboard.
A 1.0 ~ 10-3 molar stock solution of the particular catalyst compound in toluene was employed for the polymerization.

Experiment 4 to 9:
The product from example 3 in a homogeneous form was employed as the catalyst compound.
The monomer composition of the experiment, the partial pressures of the individual monomers and the reaction temperatures are shown in table 1.
Experiment 10 (comparison experiment):
(CH3)ZC cp flu ZrCI, in a homogeneous form was employed as the catalyst compound.
The monomer composition of the experiment, the partial pressures of the individual monomers and the reaction temperatures are shown in table 1.
Table 1: Compositions of the batches Ex- XetheneXpropcneXENB petheneppropenevENB vttal CtW T
peri- mn.
ment [bar][bar] [ml] [ml] [mol/I][C]

4 0.3 0.6 0.1 2.57 1.00 6.75 S 17 1 30 S 0.3 0.6 0.1 3.68 1.93 6.75 517 1 60 6 0.2 0.8 - 1.72 1.28 - S 10 1 30 7 0.2 0.8 - 2.45 2.53 - 510 1 60 8 0.4 0.6 - 3.42 1.00 - S 10 1 30 9 0.4 0.6 - 3.92 1.57 - 510 0.8 60 10 0.3 0.6 0.1 2.57 1.00 6.75 517 1 30 The polymer solutions in toluene from experiment 4-10 were removed from the reactor and stirred overnight with 200 ml aqueous 5% hydrochloric acid. The toluene phase was separated off, neutralized with SO ml saturated sodium ~WO 00/27894 PCT/EP99/08064 bicarbonate solution and washed three times with 100 ml dist. water each time.
After substantial removal of the toluene and liquid monomer on a rotary evaporator at 30°C under 40 mbar, it was attempted to precipitate the polymer by addition of 100 ml ethanol. If this was successful, the polymer was removed from the solution S and dried; if the polymer remained a highly viscous liquid, the residual toluene and monomer and the ethanol were stripped off on a rotary evaporator and the polymer was then dried. Drying was carried out overnight at 60°C under an oil pump vacuum.
Analysis of the polymer:
An Ubbelohde viscometer (capillary Oa, K = 0.005) temperature-controlled at 135°C
was used for the measurements of the weight-average viscosity M,,.
Decahydronaphthalene (Decalin), provided with 1 g/1 2,6-di-rerrbutyl-4-methylphenol as a stabilizer, was used as the solvent. The flow-through times were measured with a Viskoboy 2.
To prepare the polymer solution, 50 ml decahydronaphthalene were added to 50 mg of the polymer, the solid was dissolved overnight in a closed flask at 135°C, without stirring, and the solution was filtered hot before measurement. To clean the capillary, this was flushed twice with polymer solution. The measurements were repeated until constant values were established or until there was a number of measurement values sufficient to obtain a mean.
The molecular weights Mn for the EPM and the EPDM were calculated with the Mark-Houwink constant for PE: k = 4.75 ~ 10~, a = 0.725.

' WO 00/27894 PCT/EP99/08064 Table 2: Activities and molecular weights Mn Experiment Activity Molecular weight M,, with Scholte M,, correction [g/mol]
[g/mol]

4 1,600 72,400 no correction 1,700 45,600 no correction 6 550 75,100 95,400 7 1,900 49,200 58,900 8 1,100 110,000 128,100 9 2,700 77,800 87,800 6,700 11,500 no correction To be able to compare the molecular weights of the EP with comparison values for 5 dimethylmethylene-bridged cp flu ZrCl2 (M. Arndt, W. Kaminsky, A.-M.
Schauwienold, U. Weingarten; Macromol. Chem. Phys. 199 1135 (1988)), the correction proposed by Scholte (T. G. Scholte, N. L. J. Meijerink, H. M.
Schoffeleers, A. M. G. Brands; J. Appl. Polym. Sci. 29 (1984) 3763) was made.
The comparisons are shown in graph form in figure 1 and figure 2.
Significantly higher molecular weights compared with the literature values are to be found when the process according to the invention (4-9) is employed.
The various degrees of incorporation are shown in table 3:

Table 3: Composition of the products Experiment Incorporation Incorporation Incorporation of of of ethene propene ENB
(wt.%~ (wt.%] (wt.%]

4 38.4 52.6 9.0 53.9 34.5 11.6 6 36.2 63.8 -7 50.7 49.3 -8 57.7 42.3 -9 65.9 34.1 -A significantly better incorporation of propene is to be found in experiment 4 than in experiment 10.

The DSC measurements for determination of the melting range Tm, fusion enthalpy ~Hm and glass transition temperature Tg were carried out with a DSC 821e from Mettler-Toledo. Calibration was carried out with indium (Tm = 156.6°C).
For the measurement 5-20 mg substance were weighed into aluminium pans and measured 10 in the temperature range from -100°C to 200°C at a heating up rate of 20°C/min. Of the data obtained by heating up twice with intermediate cooling (-20°C/min), those of the second heating up were used.
The values are summarized in table 4:

~WO 00/27894 PCT/EP99/08064 Table 4: DSC values of the products Experiment Glass transitionMelting range Fusion enthalpy (2nd heating) (2nd heating) (2nd heating) [C] [C] [J/g]

4 -36 78 3.2 5 -42 106 2.0 6 -42 80 4.8 7 -52 100 10.3 8 -52 107 11.7 9 -49 113 7.5

Claims

claims

1. Process for the polymerization of ethylene, propylene and optionally a non-conjugated diene employing a metallocene as the catalyst, characterized in that the metallocene employed is a compound of the general formula (I) wherein R1 to R12 independently of one another represent H, C1-C12-alkyl, C6-C12-aryl or C7-C12-aralkyl radicals, W represents a carbon atom or an optionally substituted atom of groups 13, 15 or 16, X represents H, halogen or C1-C12 alkyl radicals, Y represents C1-C12-alkyl radicals or an optionally substituted atom of groups 14, 15 or 16 and M represents a metal of group 4, optionally in the presence of one or more co-catalysts.

2. Process according to claim 1, characterized in that Y represents a carbon atom.

3. Process according to claim 2, characterized in that W represents a carbon atom and X represents a halogen atom.

4. Process according to one or more of claims 1 to 3, characterized in that 5-ethylidene-2-norbornene or 1,4-hexadiene is employed as the non-conjugated diene.

5. Process according to one or more of claims 1 to 5, characterized in that the polymerization is carried out in solution.

6. Process according to one or more of claims 1 to 4, characterized in that the polymerization is carried out in suspension.

7. Process according to one or more of claims 1 to 4, characterized in that the polymerization is carried out in the gas phase.

8. Process according to one or more of claims 1 to 7, characterized in that the compound of the general formula (I) is employed in a supported form.

9. Process according to one or more of claims 1 to 8, characterized in that an alumoxane is employed as the co-catalyst.

10. Process according to one or more of claims 1 to 9, characterized in that one or more borates is employed as the co-catalyst.

11. Compound of the general formula (I) wherein R1 to R12 independently of one another represent H, C1-C12-alkyl, C6-C12-aryl or C7-C12-aralkyl radicals, W represents a carbon atom or an optionally substituted atom of groups 13, 15 or 16, X represents H, halogen or C1-C12 alkyl radicals, Y represents C1-C12 alkyl radicals or an optionally substituted atom of groups 14, 15 or 16 and M represents a metal of group 4.

12. Use of the ethylene/propylene copolymers or ethylene/propylene/non-conjugated diene terpolymers which can be prepared in a process according to one or more of claims 1 to 10 for the production of all types of shaped articles.