CA2263176A1 - Atactic propylene (co) polymers - Google Patents

Abstract

Atactic propylene (co)polymers may be produced in the presence of organometallic catalysts in the gas, liquid or slurry phase at -20°C to +200°C
and 1-50 bar pressure.

Organometallic compounds of transition metals for this purpose are compounds containing optionally tetrahydrogenated 2-indenyl as first ligand, of the formula (see fig. I) in which A denotes the benzo system or the tetrahydrocyclohexyl system and the further formula symbols have the meanings specified in the description.

Description

Le A 32 768-US SCJ/by/NT/V 19.01.1999 ATACTIC PROPYLENE (CO)POLYMERS
FIELD OF THE INVENTION
The present invention relates to a process for the production of amorphous, predominantly atactic propylene (co)polymers having high molecular weights in the presence of organometallic catalysts, the compounds described in more detail hereinbelow being used as such catalysts. The invention also relates to the amorphous, rubber-like polymers that can be produced in this way.
BACKGROUND OF THE INVENTION
As is known to the person skilled in the art, crystalline as well as amorphous polypropylene may be formed in the homopolymerization of propylene. Propylene polymers having an isotactic or syndiotactic structure are crystalline, whereas polypropylenes having an atactic structure are predominantly amorphous.
Amorphous polypropylene has been known for a long time and is formed as a byproduct in the production of isotactic polypropylene with Ziegler-Natta type catalysts, as is described for example in J. Polym. Sci., 1959, 34, 531. The isolation of the amorphous polypropylene that is formed in small amounts is very complicated and costly.
The use of organometallic compounds having two ligands that represent or contain the cyclopentadienyl anion (sandwich metallocenes), as catalysts for the propylene (co)polymerization is known and generally leads to propylene (co)polymers having high crystalline fractions (e.g. EP 185 918). It is also known to use organometallic compounds with only one cyclopentadienyl anion as catalysts (semi-sandwich catalysts, see for example US 5,132,380, EP 416,815, WO 91/04257, WO
96/13529).

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Semi-sandwich compounds having an indenyl ligand bridged in the 2-position are hitherto not known.
In EP 35,242 and EP 69,951 unbridged sandwich metallocenes are described that are suitable as catalysts for the production of amorphous polypropylene. The disadvantage however is that the resultant amorphous polypropylenes have low molecular weights.
Biscyclopentadienyl metal complexes that have a bridge between the two cyclopentadienyl ligands are termed ansa-metallocenes. These special metallocenes include the bisindenyl-metallocenes bridged in the 1-position at the indenyl ligand.
Such chiral ansa-metallocene derivatives are particularly suitable as catalysts for producing crystalline propylene polymers with a high isotacticity, narrow molecular weight distribution and high molecular weight, as described for example in EP
485,821 or EP 485,823.
EP 351,392 describes bridged metallocene complexes with a fluorenyl ligand and a cyclopentadienyl ligand as catalysts for the production of syndiotactic polypropylene.
US 5,596,052 describes the compound dimethylsilyl-bis(fluorenyl)-zirconium dichloride in combination with methyl aluminoxane as catalyst for producing amorphous polypropylene. Organometallic compounds that contain the fluorenyl anion as ligand are however less stable than organometallic compounds with an indenyl ligand.
Bridged biscyclopentadienyl metal complexes of titanium, zirconium and hafnium are described in Macromolecules 1955, 28, 3771 as catalysts for the production of elastomeric propylene polymers. The metal complexes that contain the cyclopentadienyl ligand and an indenyl ligand bridged in the I-position exhibit only slight catalytic activity or lead to propylene polymers of low molecular weight.

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Comparatively little is known about metallocenes with indenyl ligands bridged in the 2-position. In Organometallics 1997, 16, 3044-3050 an ansa bisindenyl hafnium complex is described, in which one of the indenyl ligands is bridged in the 2-position. This complex, dimethylsilyl-(1-indenyl)(2-indenyl)-bis-dimethylamido hafnium can undergo further reaction to dimethylsilyl-( 1-indenyl)(2-indenyl)-dimethyl hafnium. The metal complex is formed in low yield as a byproduct in a special process (vacuum, 160°C) and has to be purified in a complicated process. In Organometallics 1993, 12, 5012-5015 a multistage synthesis pathway to ethylene-bis(2-indenyl)-titanium dichloride is described. The achievable yield is very low on account of the multistage synthesis and the numerous purification operations.
On account of the synthesis pathway the number of possible structures is restricted to ethylene-bridged ligands. From WO 94/11 406 organometallic compounds of transition metals are known that contain an indenyl ligand and a cyclopentadienyl ligand, the indenyl ligand being substituted in the 2-position; this substituent can also be formed as a bridge to the second ligand. The embodiments illustrate multistage preparations having extremely unsatisfactory yields, which in the case of bridged compounds lead to 1-cyclopentadienyl-2-(2-indenyl)ethane zirconium chloride, to bis-(2-indenyl)-methane zirconium dichloride or to dimethyl-bis-(2-indenyl)silane zirconium dichloride, all of which contain impurities. In EP 3 72 414 the two compounds are named as ethylene-1-(3-but-3-enyl)inden-1-yl)-2-(( 1-but-3 -enyl)-inden-2-yl)zirconium dichloride and ethylene-1-((3-allyldimethylsilyl)-inden-1-yl)-2-((1-allyldimethylsilyl)-inden-2-yl)zirconium dichloride.
On account of the poor availability of organometallic compounds of transition metals with an indenyl ligand bridged in the 2-position, little is known of their use or their catalytic activity.

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SUMMARY OF THE INVENTION
It has now been found that such organometallic catalysts whose bridging occurs at the 2-position of at least one indenyl anion have special properties as polymerization catalysts; in fact, in the (co)polymerization of alpha-olefins, they produce predominantly atactic polymers with high molecular weights. It is, therefore, desirable to find a process for producing such catalysts bridged in the 2-position of at least one indenyl anion.
BRIEF DESCRIPTION OF THE DRAWING
Fig. 1 is a perspective view, obtained by X-ray structure analysis, of an organometallic compound of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
Accordingly, the present invention relates to a process for the production of amorphous, predominantly atactic polypropylene and amorphous propylene copolymers in the gaseous, liquid or slurry phase in the presence of organometallic catalysts at a temperature of -20°C to +200°C and at a pressure of 1-50 bar, optionally in the presence of polymerization-inert substances, which process is characterized in that an organometallic compound of transition metals with optionally, substituted 2-indenyl as first ligand, of the formula ~m ~Y (I) X~M~-Z
is used as catalyst, wherein.

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A denotes the benzo system or the tetrahydrocyclohexyl system, Q as substituent of the optionally tetrahydrogenated 2-indenyl system denotes C,-C4-alkyl, C6-C,4-aryl, C,-C,o-aralkyl, C,-C4-alkoxy, C,-C4 alkylthio, phenoxy, phenylthio, di-C,-C4-alkylamino, C6 C,4-aryl-C,-C4-alkylamino, di-C6-C14-arylamino, dibenzylamino, tri-C,-C4-alkylsilyl, di-C,-C4 alkylboranyl, phenyl-C,-C4-alkylboranyl, diphenylboranyl, di-C,-C4-alkylphosphoryl, diphenylphosphoryl or phenyl-C,-C4-alkylphosphoryl, m denotes an integer in the range from 0 to 6, M' is a transition metal of the IV, V or VI sub-group of the Mendeleev Periodic System of the Elements X denotes an anion, n is a number from 0 to 4, which is determined by the valency and the bonding state of M', Y denotes a bridge from the group comprising -C(R'Rz)-, -Si(R'Rz)-, -Ge(R'RZ),-C(R'RZ)-C(R3R4)-, -C(R'Rz)-Si(R3R4)- or -Si(R'RZ)-Si(R3R4)-, wherein R', R2, R3 and R' denote, independently of one another, hydrogen, halogen, straight-chain or branched C,-C,o-alkyl, CS-Cg-cycloalkyl, C6 C,4-aryl or C,-C,o aralkyl, and Z is a second ligand from the group comprising open-chain and cyclic, optionally anionic ~ systems, -N(RS)-, -P(R6)-, ~ N(RSR')-, ~ P(R6Rg)-, -O-, -S-, ~ ORS or ~ SRS- , the vertical line to the left of the element symbol N, P, O
or S denoting an electron pair and the bond between Z and M' having an ionic, covalent or coordinative character and wherein R5, R6, R', and Rg have, independently of one another, the same meanings as R' to R4, and RS and R' Le A 32 768-US

may in addition denote -Si(R'RZR3) and R6 and R8 may in addition denote -Si(R'RZR3), -OR', -SR', or -N(R'RZ).
The process according to the present invention is preferably carried out with organometallic compounds of the formula (I) wherein Y has the meaning -Si(R'RZ)-, -Ge(R'Rz)- or -Si(R'RZ)-Si(R3R4)-, particularly preferably -Si(R'RZ)-.
The process according to the invention is furthermore preferably carried out with non-C2-symmetrical organometallic compounds of transition metals of the formula (I) in which however instead of Z, the second ligand is Z', which denotes substituted or unsubstituted cyclopentadiene, substituted or unsubstituted 1-indene, unsubstituted 2-indene, substituted or unsubstituted fluorene, -N(RS)-, -P(R6)-, ~ N(RSR')-, P(R 6R$)-, -O-, -S-, ~ ORS- or ~ SRS-, wherein RS to Rg and the vertical line have the aforementioned meanings.
Particularly preferably organometallic compounds are used in which the second ligands are those of the formula Z" which denotes substituted or unsubstituted indenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted cyclopentadienyl, -N(RS)- or ~ N(RSR')-, especially in conjunction with Y =
-Si(R'RZ)- and M' = Ti or Zr.
Fig. 1 is a perspective view, obtained by X-ray structure analysis, of an organometallic compound that may be used according to the invention, specifically the compound tert.-butylamido-2-indenyl-dimethylsilyl-titanium dichloride.
The organometallic compounds of transition metals that may be used according to the invention, with optionally, tetrahydrogenated 2-indenyl as first ligand, of the formula Le A 32 768-US
Qm ~Y (I) X~M~-Z
wherein A, Q, m M', X, n, Y and Z have the aforementioned meanings, May, for example, be produced by reacting an optionally substituted 2-haloindene of the formula Qm p~ \ Hal~ (II) in which Hal' denotes Cl, Br or I and A, Q and m have the above meanings, at a temperature of -20°C to + 120°C with elementary Mg or Zn in an amount of 1 -100 g~atom of Mg or Zn per mole of (II) and, after separating unreacted Mg or Zn, reacting the haloindene with a dihalide of the bridge Y of the formula Hale - Y - Hal3 (III), in which Hah and Hal3 denote independently of one another Cl, Br or I, and Y has the above meanings, -g_ in an amount of 1 - 20 mole of (III) per mole of (II), with the release of MgHal'Halz or ZnHal'Hal2, wherein in the case where Y has the meaning -Si(R'RZ)-, -Ge(R'Rz)-or -Si(R'Rz)-Si(R3R°)-, the reaction of (II) with (i) Mg or Zn and (ii) with (III) may also take place simultaneously, and the reaction product of the formula Qm A ~ Y-Hal3 (IV) wherein A, Q, m, Y and Hal3 have the above meanings, is, optionally after its isolation, reacted with a Z derivative of the formula Zm2P (Va) or ZR9P (Vb), in which MZ denotes Li, Na, K or -MgHal4, wherein Hal4 has the same meanings as Halz, p denotes the number 1 or 2, R9 denotes hydrogen, -Si(R'RZR3) or Sn(R'RzR3), and Z, R~, R2 and R; have the above meanings, with the release of a compound of the formula MZHal3 (VIa) or R''Hal~ (VIb), Le A 32 768-US

in which MZ, R9 and Hal3 have the above meanings, optionally, in the presence of an auxiliary base, to form the 2-indenyl compound of the formula Qrr, /~ \ Y-Z (VII) in which A, Q, m, Y and Z have the above meanings and which may be present as a dianion, and in which Z may furthermore carry MZ, R9 or an electron pair, and is then reacted further with a transition metal compound of the formula M'Xq (VIII) in which M' and X have the above meanings and q is a number from 2 to 6, which depends on the oxidation state of M'.
Open-chain and cyclic ~-systems within the scope of the meaning of Z are, for example, butadiene, isoprene, chloroprene, substituted or unsubstituted cyclopenta-diene, substituted or unsubstituted 1-indene, substituted or unsubstituted 2-indene, or substituted or unsubstituted fluorene, which may be covalently bonded to the bridge Y and ionically, covalently or coordinatively bonded to M'. Substituents of the ~-Le A 32 768-US

systems may, independently of Q, have the same meanings as Q, and may, independently of m, likewise be present m times. Preferably, the aforementioned systems are cyclic ~-systems, particularly preferably, 2-indenyl.
Within the scope of the specified meaning of A, the first ligand in (I) denotes 2-indenyl or 2-tetrahydroindenyl, preferably, 2-indenyl.
Straight-chain or branched C,-C,o-alkyl is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert.-butyl, the isomeric pentyls, hexyls, octyls, or decyls.
C,-C4-alkyl is preferred, methyl and ethyl being particularly preferred.
CS-C8-cycloalkyl is, for example, cyclopentyl, methylcyclopentyl, dimethyl-cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl, cyclooctyl, preferably cyclopentyl and cyclohexyl and their methyl and dimethyl 1 S derivatives.
C6-C,4-aryl is, for example, phenyl, naphthyl, biphenylyl, anthryl, phenanthryl, or preferably phenyl.
C,-C,o-aralkyl is, for example, benzyl, a- or (3-phenylethyl, phenylpropyl or phenylbutyl.
C,-C4-alkoxy and C,-C4-alkylthio are, for example, methoxy, methylthio, ethoxy, ethylthio, propoxy, propylthio, isopropoxy, isopropylthio, butoxy, butylthio, isobutoxy and isobutylthio.
Aryl and the aromatic parts of aralkyl may be singly or doubly substituted, identically or differently, by fluorine, chlorine, bromine, methyl, ethyl, methoxy or ethoxy.

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Halogen, within the scope of R' to R8, is for example, fluorine, chlorine, bromine or various of the latter, preferably chlorine.
M' is, for example, Ti, Zr, Hf, V, Nb, Ta, Cr, W, Mo; preferably Ti, Zr, Hf, F, Nb;
particularly preferably Ti, Zr, Hf, and most particularly preferably Ti, Zr.
M' may be used in the highest possible oxidation state as well as in a lower oxidation state different therefrom, and may appear as such in the organometallic compounds.
In many cases, it is advantageous to use M' first of all in a lower oxidation state and then to oxidize it to a higher state using a mild oxidizing agent, for example, PbClz.
X is a singly or multiply charged anion from the group comprising chloride, bromide, iodide, C,-C4-carboxylate, amide, C,-C4-alkyl, phenyl, benzyl, neopentyl and butadienyl, preferably chloride or bromide, and various of the aforementioned anions may also be present.
Hal', Halz and Hal3 within the scope of (II) and (III) are, independently of one another, Cl, Br or I, and preferably Hal' is Br and Hale and Hal3 are Cl or Br.
The temperature of the reaction of (II) with Mg or Zn is in the range from -20°C to +120°C, preferably 0°C to +100°C, particularly preferably +25°C to +80°C.
The amount of Mg or Zn is 1 to 100 g~atom per mole of (II). In principle, amounts outside the aforementioned ranges may also be used. Below 1 g~atom of Mg or Zn per mole of (II), the conversion of (II) is incomplete, while amounts above g atom provide no further advantage with regard to the completeness and velocity of the reaction. Preferably, amounts of 1 to 10 g atom of Mg or Zn, particularly preferably 1 to 5 g atom of Mg or Zn per mole of (II) are used. Of the metals, Mg and Zn, Mg is preferred for the reaction.

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The temperature for the further reaction with (III) is likewise in the range from -20°C to +120°C, preferably 0°C to +100°C, and particularly preferably +25°C to +80°C.
The amount of (III) is 1 to 20 moles per mole of (II). The same comments apply to amounts outside this range as were mentioned above in connection with the amount of Mg or Zn. Preferably, 1 to 10 moles of (III), particularly preferably, 1 to 2 moles of (III) are used per mole of (II).
Unreacted Mg, Zn and (III) are separated from the reaction mixture in a manner known to the person skilled in the art and may be reused.
The production of the organometallic compounds that may be used according to the present invention may be carried out in the presence of a polar, aprotic solvent.
Suitable solvents are, for example, methylene chloride, chloroform, dimethyl-formamide, N-methylpyrrolidone and ethers; of the aforementioned compounds, ethers are preferred, for example diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, and other ethers known to the person skilled in the art. The amount of solvent is chosen so that (II) and the organo-Mg and organo-Zn compound formed therefrom, are present in dissolved form and the unreacted Mg or Zn can be separated, for example, by filtration or decanting or similar separation operations.
This amount is for example 50 to 1000% of the amount of (II).
Y is preferably -C(R'RZ)-, -Si(R'RZ)-, particularly preferably -Si(R'R2)-.
In the case where Y has the meaning -Si(R'R2)-, -Ge(R'Rz )- or -Si(R'RZ)-Si(R3R4)-, the simultaneous reaction of (II) with (i) Mg or Zn and (ii) with (III) provides an elegant way of economizing on a reaction stage.
In the case where the reaction of (IV) with (Va) or (Vb) to form (VII) is carried out in the presence of an auxiliary base, the following may for example, be used for this Le A 32 768-US

purpose: open-chain or cyclic tertiary aliphatic amines with a total of 3 to atoms, such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, triisobutyl-amine, trihexylamine, trioctylamine, tridecylamine, N-methylpiperidine, N,N'-dimethylpiperazine, diaza-bicyclononane (DBN), diaza-bicyclooctane (DABCO), diaza-bicycloundecane (DBU), and also amines with variously long C chains, such as N,N-dimethylbutylamine, N,N-dimethyloctylamine, N,N-dimethylstearylamine and the like, and aromatic amines such as pyridine, methylpyridines, quinoline, N,N-dimethylaniline, and the like.
The reaction mixture containing the organometallic compound (I) may be worked up using operations known to the person skilled in the art, such as filtration, distilling off volatile components of the mixture, and crystallization.
The compounds of the formula (I) are frequently used in combination with co-catalysts for the (co)polymerization according to the present invention. As co-catalysts there may be used the co-catalysts known in the field of metallocene chemistry, such as polymeric or oligomeric alumoxanes, Lewis acids, as well as aluminates and borates. In this connection, reference should be made, in particular, to Macromol. Symp. Vol. 97, July 1995, pp.l - 246 (for alumoxanes), as well as to EP
277,003, EP 277,004, Organometallics 1997, 16, 842-857 (for borates) and EP
573,403 (for aluminates). Particularly suitable as co-catalysts are methyl alumoxane, methyl alumoxane modified by triisobutyl aluminum (TIBA), as well as diisobutyl alumoxane, trialkyl aluminum compounds such as trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, triisooctyl aluminum, furthermore, dialkyl aluminum compounds such as diisobutyl aluminum hydride, diethyl aluminum chloride, substituted triaryl boron compounds such as tris(pentafluorophenyl)borane, as well as ionic compounds that contain tetrakis(pentafluorophenyl) borate as anion, such as triphenylmethyl tetrakis(pentafluorophenyl) borate, trimethylammonium tetrakis(penta-fluorophenyl) borate, N,N-dimethylanilinium tetrakis(pentafluoro-phenyl) borate, substituted triaryl aluminum compounds such as tris(penta-fluorophenyl) aluminum, as well as ionic compounds that contain tetrakis(penta-i Le A 32 768-US

fluorophenyl)aluminate as anion, such as triphenylmethyl tetrakis(pentafluorophenyl) aluminate, and N,N-dimethylanilinium tetrakis(pentafluorophenyl) aluminate.
It is obviously possible to use the co-catalysts mixed with one another. The appropriate mixing ratios should be determined in each case by suitable preliminary experiments.
The (co)polymerization according to the present invention is carried out in the gaseous, liquid or slurry phase. The temperature range is from -20°C to +200°C, preferably 0°C to 160°C, particularly preferably +20°C to +80°C; the pressure range is from 1 to 50 bar, preferably 3 to 30 bar. Polymerization-inert solvents that are used are, for example, saturated aliphatic or (halogen)aromatic compounds, such as pentane, hexane, heptane, cyclohexane, petroleum ether, paraffin oil, hydrogenated benzines, benzene, toluene, xylene, ethylbenzene, chlorobenzene and the like.
These reaction conditions for the (co)polymerization are, in principle, known to the person skilled in the art.
Suitable comonomers are CZ- to C,o alkenes, such as ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, isobutylene, and arylalkenes, for example styrene.
Suitable comonomers also include conjugated dimes such as 1,3-butadiene, isoprene, 1,3-pentadiene, and non-conjugated dimes such as 1,4-hexadiene, 1,5-heptadiene, 5,7-dimethyl-1,6-octa-dime, 4-vinyl-1-cyclohexene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene and dicyclopentadiene.
The propylene (co)polymers produced by the process according to the present invention have molecular weights of M", > 100,000 g/mole and molecular weight distributions of M,~,/M~<4. The propylene (co)polymers according to the present invention, have intrinsic viscosities greater than 1 dl/g. The crystallinities are less than 10%, the percentage crystallinity being defined as (enthalpy of fusion/209 J/g) x 100 and the enthalpy of fusion in Jlg being determined by the DSC method.
Particularly preferred are propylene (co)polymers with enthalpies of fusion of less Le A 32 768-US

than 5 J/g (DSC method). The propylene (co)polymers are readily soluble in conventional solvents such as hexane, heptane, diethyl ether or toluene.
Rubbers based on propylene and one or more of the aforemen-boned comonomers may, in particular, also be produced by the process according to the invention.
Particularly preferred is the copolymerization of ethylene and propylene, amorphous propylene (co)polymers with an ethylene fraction in the polymer in the range from 1 to 70 wt.%, preferably 10 to 65 wt.%, being obtained.
EPDM rubbers based on ethylene, propylene and a dime, preferably 5-ethylidene-norbornene can also be produced by the process according to the invention. The EPDM rubbers are characterized in that they have high molecular weights and small crystalline fractions.
For example, the (co)polymerization of propylene with or without the aforementioned comonomers may be performed as follows: a steel autoclave is first cleaned in a conventional way and then filled with a solvent and a scavenger, for example triisobutyl aluminum. Possible impurities and catalyst poisons, for example, water or other oxygen-containing compounds, are rendered harmless by the scavenger. A compound of the formula (I) is then added as catalyst precursor.
The reactor is next filled with monomers to a specific pressure, thermostatically controlled to a selected temperature, and the polymerization is initiated by adding one or more of the aforementioned co-catalysts. The polymerization may be carried out in a continuous or batchwise process.
The invention is further illustrated but is not intended to be limited by the following examples in which all parts and percentages are by weight unless otherwise specified.

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F.X A MP1,FC
The invention is illustrated in more detail with the aid of the following examples.
General instructions: Organometallic compounds were produced and handled under the exclusion of air and moisture and under an argon shield, (Schlenk technique). All required solvents were rendered perfectly anhydrous before use by boiling far several hours over a suitable drying agent, followed by distillation under argon. The compounds were characterized by ' H-NMR, '3C-NMR and mass spectroscopy.
Polymer characterization The intrinsic viscosity was determined in an Ubbelohde capillary viscosimeter at 140°C in o-dichlorobenzene as solvent (multipoint measurement). The molecular weight distribution was determined in a WATERS 150 CV plus Gel Permeation Chromatograph at 140°C in o-dichlorobenzene. The DSC measurements were performed in a Perkin-Elmer DSC-2 differential scanning calorimeter according to the following procedure: two beatings, -90°C to +180°C, heating rate 20K/min, rapid cooling at a rate of 320 K/min to -90°C, flushing with nitrogen, and weighing a 12.3 mg sample in standard capsules. The Mooney viscosity was determined according to ASTM 1646 / DIN 52 523. The IR spectroscopic determination of the polymer composition was performed according to ASTM D 3900.
Example 1 Preparation of chloro-2-indenyldimethylsilane 2-bromoindene (4.0 g, 0.02 moles) was dissolved in 4 ml of tetrahydrofuran and added dropwise to a mixture consisting of magnesium (0.738, 0.03 moles) and dichlorodimethylsilane (S.Og, 0.04 moles) in 4 ml of tetrahydrofuran. The solution boiled gently. After 15 hours of stirring the volatile constituents were removed in an oil pump vacuum and 40 ml of n-pentane was added to the residue. The desired Le A 32 768-US

product was suctioned filtered from the precipitated magnesium salt. After removing the solvent in an oil pump vacuum 4.6g (95%) of chloro-2-indenyldimethylsilane was obtained as a colorless oil.
' H NMR (CDC13): 8 7.3 - 7.6 (m, 4H, Ind), 7.29 (s, 1 H, Ind), 3 .65 (s, 2H, CHZ), 0.74 (s, 6 H, SiMe2).
13~ NMR (CDC13): 8 146.4. (C;~d, [C-Si]), 144.6 (C;"d, [C]), 143.2 (CH=CSi), 126.3 Carom. CH, Ind), 125.6 Carom. CH, Ind), 123.70 Carom. CH, Ind), 121.8 Carom.
CH, Ind), 41.5 (CHz), 2.0 (SiMe).
Example 2 Preparation of cyclopentadienyl-2-indenyl-dimethylsilane Chloro-2-indenyldimethylsilane (4.6 g, 0.022 moles) from Example 1 was dissolved in 20 ml of diethyl ether. The solution was cooled to 0°C and a solution of cyclopentadienyl sodium ( 1.94 g, 0.022 moles) in 20 ml of tetrahydrofuran was added dropwise. The mixture was stirred for 15 hours at 25°C. 50 ml of water was then added, and the organic phase was washed again with water and dried over NazS04. After removing the solvent in an oil pump vacuum the remaining pale yellow oil was purified by column chromatography. After removing the solvent 2.4 g (46%) of cyclopentadienyl-2-indenyldimethylsilane was obtained as a colorless oil.
'H NMR (CDCl3): b 7.6 - 7.3 (m, 4H, arom. H), 7.01 (s, 1 H, Ph-CH=C(SiMeZCp)), 6.72 (m, 4H, Cp), 3.56 (s, 2H, CH2, Ind), {3,67, 3,49, 3,18 } (s, 1 H, CH-Si, Cp), {0.57, 0.51, 0.26} (s, 6H, Si-(CH3)2).
'3C NMR (CDCl3): 8 146.5 (C), 145.1 (C), 141.8 (Ph-CH=C(SiMe2Cp)), 137.9 (Ph C(SiMe2Cp)=CH), 132.9 (broad, CH, Cp), 130.5 (broad, CH, Cp), 126.2 (CH, Ind.)., 124.9 (CH, Ind.), 123.5 (CH, Ind), 120.9 (CH, Ind), 51.1 (broad, CH-Si, Cp), 45.3 (broad, CH-Si, Cp), 42.6 (CHZ, Ind), -3.9 (SiMe).

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Example 3 Preparation of cyclopentadienyl-2-indenyldimethylsilyl zirconium dichloride Cyclopentadienyl-2-indenyldimethylsilane (l.Og, 0.0042 moles) from Example 2 was dissolved in 10 ml of tetrahydrofuran and 10 ml of diethyl ether and reacted at -40°C
with a 2.5 molar solution of n-butyl lithium in hexane (3.5 ml, 0.0084 moles).
The reaction mixture was stirred for 15 hours at 25°C. The solvents were then removed in an oil pump vacuum and the residue was washed with 20 ml of petroleum ether.
The thus purified dilithium salt was suspended in a further 20 ml of petroleum ether.
ZrC14.2 THF (1.58 g, 0.042 moles) was likewise suspended in 20 ml of toluene and added in one portion at 25°C to the dilithium salt. After 30 minutes a yellow-orange coloration was detectable, which became increasingly darker. After 15 hours of stirring the solvents were removed in an oil pump vacuum and the residue was extracted with 80 ml of toluene and freed from insoluble constituents by filtration over kieselguhr. The toluene was removed in an oil pump vacuum. 1.08 g (64%) of cyclopentadienyl-2-indenyldimethylsilyl zirconium dichloride was obtained as a yellow-orange solid.
'H NMR (CDC13): b 7.63 (dd, 2H, ZJHH = 3.0, 5.0 Hz, Ind), 7.30 (dd, 2H, ~JHH
3.0, 5.0 Hz, Ind), 6.90 (pt, 2 H, ZJ~ = 0.9 Hz, Cp), 6.16 (s, 2 H, Ind), 6.05 (pt, 2 H, zJ~ 0.9 Hz, Cp), 0.83 (s, 6H, SiMez).
Example 4 Preparation of a solution of lithium fluorene Fluorene (2.2 g, 0.0136 moles) was dissolved in 40 ml of diethyl ether and reacted at 0°C with a 2.5 molar solution of n-butyl lithium in hexane (5.5 ml, 0.0136 moles).
After 4 hours of stirring at 25 °C the volume of the solution was reduced to half in an oil pump vacuum.

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Example 5 Preparation of fluorenyl-2-indenyldimethylsilane A solution of lithium fluorene from Example 4 was added slowly at 0°C
through a septum and injection syringe to a solution of chloro-2-indenyldimethylsilane (2.85 g, 0.0136 moles) according to Example 1 in 20 ml of diethyl ether. After 2 hours of stirring at 25°C, the reaction product was filtered off from the precipitated LiCI. The solvent was removed from the filtrate and the colored residue was dissolved by heating in etherlpetroleum ether and then crystallized at -30°C. 3.45 g (75%) of fluorenyl-2-indenyldimethylsilane was obtained as a colorless solid. m.p.:
125°C.
'H NMR (CDCl3): 8 7.9 - 7.8 (m, 2 H, arom. H), 7.5 - 7.2 (m, 12 H, arom. H), 7.04 (s, 1 H, Ind), 4.10 (s, 1 H, CH, Flu), 3.29 (s, 1 H, CH2, Ind), 0.20 (s, 6 H, SiMe2).
~3C NMR (CDCl3):: 8 147.4 (C;"a, [C]), 146.0 (C;"a, [C], 146.0 (C;"a, [C-Si]), 145.7 (C~,u, [C]), 143.2 (CH=CSi), 141.1 (C"u, [C]), 126.8 (CH, arom.'), 126.6 (CH, arom.), 125.9 (CH, arom.), 125.5 (CH, arom.), 124.7 (CH, arom.), 124.2 (CH, arom.), 121.6 (CH, arom.), 120.5 (CH, arom.), 43.4 (CHSi, Flu), 46.5 (CH2, Ind), -3.4 (SiMe2).
Example 6 Preparation of fluorenyl-2-indenyldimethylsilyl zirconium dichloride Fluorenyl-2-indenyldimethylsilane (1.33 g, 0.004 moles) from Example 5 was dissolved in a mixture of 10 ml of tetrahydrofuran and 30 ml of diethyl ether and reacted at -40°C with a 2.5 molar solution of n-butyl lithium in hexane (3.2 ml, 0.008 moles). The reaction mixture was stirred for 15 hours at 25°C. The solvents were then removed in an oil pump vacuum and the residue was washed with 20 ml of petroleum ether. The, thus, purified dilithium salt was suspended in a further 20 ml of petroleum ether. ZrCl4 (0.815 g, 0.0035 moles) was suspended in 20 ml of petroleum ether and added to the dilithium salt at 25°C. After 15 hours of stirring, the solvents were removed in an oil pump vacuum and the residue was extracted with 80 ml of CHZCI~ and also freed from insoluble constituents by filtration through Le A 32 768-US

kieselguhr. The CHZCIz was evaporated in an oil pump vacuum. 1.90 g (95%) of an orange-colored solid was obtained.
'H NMR (CDCl3): 8 8.15 (d, 2 H, 3J,~, = 2 Hz, arom.), 7.70 (d, 2 H, 3J~ = 2 Hz, arom.), 7.6 (m, 2 H, Ind), 7.4-7.1 (m, 6 H, arom), 6.05 (s, 2 H, 2-Ind), 1.21 (s, 6H, SiMez).
Example 7 Preparation of {trimethylsilylcyclopentadienyl}-2-indenyl-dimethylsilane Chloro-2-indenyldimethylsilane (5.15 g, 0.025 moles) according to Example 1 was dissolved in 10 ml of tetrahydrofuran. The solution was cooled to 0°C
and a solution of trimethylsilylcyclopentadienyl lithium (3.60 g, 0.025 moles) in 20 ml of tetrahydrofuran was added. The reaction mixture was stirred for 15 hours at 25°C.
50 ml of water was then added, and the organic phase was washed again with water and dried over Na2S04. After removing the solvents in an oil pump vacuum, the remaining yellowish oil was purified by means of column chromatography. After removing the solvents 2.12 g (34%) of (trimethylsilylcyclopentadienyl)-2-indenyl-dimethylsilane was obtained as a colorless oil.
' H NMR (CDCl3):: 8 7.6 - 7.4 (m, 2 H, arom. H), 7.3 - 7.2 (m, 2 H, arom. H), 7.14 (s, 1 H, Ind), 6.77 (pt, 2 H, 3J = 0.5 Hz, Cp), 6.68 (pt, 2 H 3J - 0.5 Hz, Cp), 3.42 (s, 2 H, CHz, Ind), 0.26 (s, 6 H), SiMe2), -0.06 (s, 9H SiMe3).
"H NMR (CDC13): 8 147.2 (C;~d, [C]), 146.6 (C;nd, [C]), 145.1 (C;~d, [C-Si]), 141.8 (CH=CSi, Ind), 135.7 (CH, Cp), 130.9 (CH, Cp), 126.6 (CH, arom., Ind), 124.7 (CH, arom., Ind), 123.4 (CH, arom., Ind), 120.8 (CH, arom., Ind), 43.4 (CHZ, Ind), 39.1 (C=CSi2, Cp), -0.9 (SiMe3), -1.9 (SiMez).

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a Example 8 Preparation of {trimethylsilylcyclopentadienyl}-2-indenyl-dimethylsilyl zirconium dichloride {Trimethylsilylcyclopentadienyl}-2-indenyl-dimethylsilane (0.931 g, 0.003 moles) from Example 7 was dissolved in 30 ml of diethyl ether and reacted at -40°C with a 2.5 molar solution of n-butyl lithium in hexane (2.4 ml, 0.006 moles). The reaction mixture was stirred for 15 hrs at 25°C. The solvents were then removed in an oil pump vacuum and the residue was washed with 20 ml of petroleum ether. The thus purified dilithium salt was suspended in a further 20 ml of petroleum ether.
ZrCl4 (0.815 g, 0.0035 moles) was likewise suspended in 40 ml of petroleum ether and added to the dilithium salt at 25°C. After 15 hours of stirring, the solvents were removed in an oil pump vacuum and the residue was extracted with 80 ml of methylene chloride and freed from the insoluble constituents by filtration through kieselguhr. The methylene chloride was evaporated in an oil pump vacuum. 0.747 g (53%) of the title compound was obtained as a pale yellow solid. m.p.
85°C.
'H NMR (CDCl3): 7.70 (d, 1 H, 3J,~ = 2.0 Hz, Ind.), 7.47 (d, 1 H, 3JHH = 2.0 Hz, Ind.), 7.3 (m, 2 H, Ind), 7.06 (s, 1 H, Ind), 6.33 (pt, 1 H 3J~, = 0.5 Hz, Cp) 6.17 (pt, 1 H, 3J,~ = 0.5 Hz, Cp), 6.15 (pt, 1 H, 3J~ = 0.5, Cp), 6.02 (s, 1 H, Ind), 0.86 (s, 3 H, SiMe), 0.77 (s, 3 H, SiMe), 0.23 (s, 9 H, SiMe3).
"H NMR (CDC13): 8 150.0 (C), 135.8 (CH), 135.3 (C), 131.4 (C), 126.8 (CH), 126.0 (CH), 125.1 (CH), 125.0 (CH), 122.3 (CH), 116.4 (CH), 112.2 (C), 110.7 (C), 109.6 (CH), 101.7 (CH) -0.39 (SiMe3)-3.9 (SiMe), -5.9 (SiMe).
Example 9 Preparation of 1-indenyl-2-indenyldimethylsilane Chloro-2-indenyldimethylsilane (4.95 g, 0.023 moles) according to Example 1 was dissolved in 20 ml of diethyl ether. The solution was cooled to 0°C and a solution of lithium indene ( 1.94 g, 0.022 moles) in 25 ml of diethyl ether was added dropwise.
The reaction mixture was stirred for two hours at 25°C and then heated under reflux.

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The reaction product was worked up by adding 60 ml of water and the organic phase was washed once more with water and dried over NazS04. After removing the solvents in an oil pump vacuum the remaining pale yellow oil was purified by means of column chromatography. 3 .23 g (47%) of 1-indenyl-2-indenyldimethylsilane was obtained as a colorless oil that crystallized at 4°C in a refrigerator.
m.p.:45°C.
' H NMR(CDCI3): 8 7.9 - 7.8 (m, 2 H, Ind), 7.7 - 7.5 (m, 2 H, Ind), 7.48 (s, 1 H, Ind), 7.35 (d, 1 H, 3J = 2.0 Hz, Ind), 7.03 (d, 1 H, 3J= 2.0 Hz, Ind), 4.06 (s, 1 H, CH), 3.69 (s, 1 H CH2), 3.64 (s, 1 H, CHZ), 0.58 (s, 3 H, SiMe2), 0.52 (s, 3 H, SiMez).
" C NMR (CDCI3): 8 147.5 (C;~d., [C]), 146.6 (C,~d, [C]), 146.0 (C;"d, [C]), 145.7 (C;~d, [C]), 145.7 (C;"d, [C]), 143.2 (CH = CSi), 136.2 (CH = CSi), 130.2. (CH
= CSi), 127.2 Carom. CH, Ind), 125.9 Carom. CH, Ind), 124.6 Carom. CH, Ind), 124.5 Carom.
CH, Ind), 124.5 Carom. CH, Ind), 123.7 Carom. CH, Ind), 121.9 Carom. CH, Ind), 121.9 Carom. CH, Ind), 46.5 (CH -Si), -2.9 (SiMe), -3.27 (SiMe).
Example 10 Preparation of 1-indenyl-2-indenyldimethylsilyl zirconium dichloride The compound 1-indenyl-2-indenyldimethylsilane ( 1.0 g, 0.003 5 moles) from Example 9 was dissolved in a mixture of 5 ml of tetrahydrofuran and 30 ml of diethyl ether and reacted at -40°C with a 2.5 molar solution of n-butyl lithium in hexane (2.8 ml, 0.007 moles). The reaction mixture was stirred for 15 hours at 25°C. The solvents were then removed in an oil pump vacuum and the residue was washed with 20 ml of petroleum ether. The thus purified dilithium salt was suspended in a further 20 ml of petroleum ether. ZrCl4 (0.815 g, 0.0035 moles) was likewise suspended in 20 ml of toluene and added to the dilithium salt at 25°C. After 15 hours of stirring, the solvents were removed in an oil pump vacuum and the residue was extracted with ml of CHZC1, and freed from insoluble constituents by filtration through kieselguhr.
The CHZCIz was evaporated in an oil pump vacuum. 1.59 g (96%) of 1-indenyl-2-indenyldimethylsilyl zirconium dichloride was obtained as an orange-colored solid.
'H NMR (CDCl3): 8 7.6 - 7.5 (m, 2 H, Ind), 7.4 - 7.3 (m, 2 H, Ind), 7.2 - 7.1 (m, 4 H, Ind), 7.01 (d, 1 H, ~J"H = 0.75 Hz, 1-Ind), 6.20 (d, 1 H, 'J,iH = 0.75 Hz, 1-Ind), 6.20 (d, Le A 32 768-US

1 H, 3J,~, = 0.75 Hz, 1-Ind), 6.13 (s, 1 H, 2-Ind), 6.10 (s, 1 H, 2-Ind), 1.11 (s, 3H, SiMe), 0.89 (s, 3H, SiMe).
'3C NMR (CDCl3): 8 135.3 (C), 133.8 (C), 131.3 (C), 127.5 (CH), 126.6 (CH), 126.4 (CH), 126.2 (CH), 125.3 (CH), 124.8 (CH), 124.4 (CH), 120.0 (CH), 118.1 (CH), 110.2 (C), 107.1 (CH), 103.8 (CH), 91.78 (C), -2.4 (SiMe), -4.6 (SiMe).
Example 11 Preparation of the catalyst solution 18.1 mg (40 pmoles) of 1-indenyl-2-indenyldimethylsilyl zirconium dichloride from Example 10 was dissolved in 19 ml of toluene, 1 ml of methyl alumoxane (MAO in toluene, from Witco) was added thereto, and the catalyst was preactivated for mins at 20°C.
Polymerization of propylene 100 ml of toluene and 5 ml of a 10% solution of methyl alumoxane (MAO in toluene, from Witco) were placed in a 250 ml glass reactor and heated to 40°C.
Propylene was then continuously passed into the solution at a pressure of 1.1 bar through a gas inlet tube. The polymerization was initiated by adding 5 ml of the preactivated catalyst solution (= 10 pmoles of 1-indenyl-2-indenyldimethylsilyl zirconium dichloride). After 1 hour of polymerization at a temperature of 40°C and a propylene pressure of 1.1 bar, a clear reaction solution was obtained, and the polymerization was then stopped by addition of 100 ml of methanol. The precipitated elastic polymer was filtered off, washed with methanol and dried in a vacuum drying cabinet. 12.2 g of solid amorphous polypropylene were obtained.

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Example 12 Comparison example The polymerization of Example I 1 was repeated, except that instead of the 1-indenyl-2-indenyldimethylsilyl zirconium dichloride, dimethylsilyl-bis( 1-indenyl)-zirconium dichloride in the form of the racemate was used as catalyst component.
The polypropylene precipitated out as a white precipitate already during the poly-merization. 13.4 g of crystalline polypropylene powder was obtained having a melting point of 145°C.
Example 13 Preparation of 'butylamine-2-indenyldimethylsilane Chloro-2-indenyldimethylsilane (4.7 g, 0.02 moles), according to Example 1, was dissolved in 20 ml of diethyl ether and added at 25°C to a solution of 'BuNH2 ( 10 ml, 0.2 moles) in 50 ml of diethyl ether, with the formation of a suspension. After 12 hours of stirring, the solvent was removed in an oil pump vacuum and the residue was taken up in 40 ml of n-pentane. Precipitated 'BuNHz HCI was separated by filtration. After removing the n-pentane, 5.2 g (97%) of 'butylamine-2-indenyldimethylsilane was obtained as a colorless oil.
'H NMR (CDCl3): 8 7.5 - 7.4 (m, 2 H, Ind), 7.3 - 7.2 (m, 2 H, Ind), 7.18 (s, 1 H, Ind), 3.52 (s, 2 H, CHZ), 1.20 (s, 9 H, C(CH3)3), 0.78 (s, broad, NH), 0.32 (s, 6 H, SiMez).
'3C NMR (CDCl3): 8 151.0 (C;"d, [C-Si]), 146.9 (C;"d, [C]), 145.8 (C;"a, [C]), 140.9 (CH=CSi), 126.2 Carom. CH, Ind), 124.7 Carom. CH, Ind), 123.7 Carom. CH, Ind), 120.9 Carom. CH, Ind), 49.5 (C(CH3)3), 42.3 (CHZ), 33.7 (C(CH3)3), 1.1 (SiMe).

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Example 14 Preparation of 'butylamido-2-indenyldimethylsilyl zirconium dichloride Tert-butylamido-2-indenyldimethylsilane ( 1.5 g, 0.0061 moles) from Example 13 was dissolved in 30 ml of diethyl ether and 5.0 ml of a solution of n-butyl lithium in hexane (2.5 moles) was added dropwise thereto at -30C. A colorless suspension was formed, which was stirred for 15 hours at 25 °C. The diethyl ether was then evaporated in vacuo and the remaining salt was washed twice, each time with 30 ml of n-pentane, and re-suspended in 20 ml of n-pentane. ZrCl4 ( 1.41 g, 0.006 moles) in 40 ml of toluene was added at 25°C to this suspension. During the addition of ZrCl4, the reaction solution quickly became yellow-orange in color. The solution was stirred for 15 hours. The product was worked up by removing the solvent in an oil pump vacuum and extraction with 70 ml of CHZCIz. 0.72 g (29%) of 'butylamido-2-indenyldimethylsilyl zirconium dichloride was obtained as a yellow powder.
'H NMR (CDCI,): 8 7.74-7.71 (dd,3JHH = 1.0 Hz, 1.5 Hz, 2 H, Ind), 7.42-7.39 (dd, 3J~ = 1.0 Hz, 1.5 Hz, 2 H, Ind), 6.70 (s, 2 H, Ind), 1.38 (s, 9 H, C(CH3)3), 0.67 (s, 6 H, SiMe2).
'3 C NMR (CDCl3): b 134.2 (C), 128.1 (CH, 123.4 (CH), 119.7 (CH), 114.6 (C-Si), 65.2 (C(CH3)3), 32.8 (C(CH3)3), 0.85 (Si-CH3).
Example 15 Preparation of the catalyst solution 17.2 mg (42.4 p.moles) of 'butylamido-2-indenyldimethylsilyl zirconium dichloride from Example 14 was dissolved in 20.2 ml of toluene and preactivated with 1 ml of a 10% solution of methyl aluminoxane (MAO in toluene, from Witco).
Copolymerization of ethylene and propylene 100 ml of toluene and 5 ml of a 10% solution of methyl alumoxane (MAO in toluene, from Witco) were placed in a 250 ml glass reactor. An ethylene/propylene Le A 32 768-US

mixture (mass ratio 1:2) was then passed continuously into the solution at 20°C and 1.1 bar pressure through a gas inlet tube. The polymerization was initiated by adding 0.5 ml of the preactivated catalyst solution (= 1 pmole 'butylamido-2-indenyldi-methylsilyl zirconium dichloride). After 1 hour of polymerization at a temperature of 20°C and a pressure of 1.1 bar a clear reaction solution was obtained, and the polymerization was stopped by adding 100 ml of methanol. The precipitated elastic polymer was filtered off, washed with methanol and dried in a vacuum drying cabinet. 2.3 g of amorphous copolymer was obtained. The IR spectroscopic determination of the composition of the copolymer revealed an incorporation of 63.7 wt.% of ethylene and 36.3 wt.% of propylene.
Example 16 Preparation of 'butylamido-2-indenyldimethylsilyl titanium dichloride Tert-butylamin-2-indenyl-dimethylsilane (1.0 g, 0.0041 moles) from Example 13 was dissolved in 20 ml of n-pentane, and 3.4 ml of a solution of n-BuLi in hexane (2.5 molar) was added dropwise thereto at 0°C. A suspension was formed, which after 1 S hours of stirring, agglomerated to form a resinous mass. The n-pentane was evaporated in vacuo and the remaining yellowish powder was dissolved at -78°C in 20 ml of tetrahydro-furan and transferred by means of a cannula to a suspension of TiCl33 THF in 10 ml of tetrahydrofuran at -78°C. A deep yellow coloration was then observed. When the temperature of the suspension reached room temperature, solid PbClz ( 1.13 g, 0.0041 moles) was added and the mixture was stirred for 0.5 hour. The suspension now turned a reddish-brown color. The solvent was removed and the remaining powder was extracted three times, each time with 20 ml of toluene.
After adding the toluene and briefly stirring, the suspension was allowed to settle and the supernatant liquid was pipetted off. The toluene was now removed from the extract and replaced by n-pentane, 1.06 g (71.9%) of 'butylamido-2-indenyldimethylsilyl titanium dichloride precipitating as a reddish-brown solid. Single crystals were obtained by crystallization from methylene chloride at -30°C. An X-ray structure analysis was carried out (Fig. I ). Melting point: 143°C.

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1 H NMR (CDC13): 8 7.74-7.71 (dd,3JHH = 1.0 Hz, 1.5 Hz, 2 H, Ind), 7.42-7.39 (dd, 3JHH = 1.0 Hz), 1.5 Hz, 2 H, Ind), 6.78 (s, 2 H, Ind), 1.41 (s, 9 H, C(CH3)3), 0.77 (s, 6 H, SiMez).
'3 C NMR (CDCl3): 8 134.2 (C), 128.1 (CH), 124.4 (CH), 119.7 (CH)), 114.6 (C-Si), 65.2 (C(CH3)3), 32.3 (C(CH3)3), 0.0 (Si-CH3).
Example 17 Preparation of the catalyst solution 27 mg (74.5 moles) of 'butylamido-2-indenyldimethylsilyl titanium dichloride from Example 16 was dissolved in a mixture of 1.9 ml of triisobutyl aluminum and 13 ml of hexane.
Polymerization of propylene 500 ml of hexane, 0.1 ml of triisobutyl aluminum (TIBA) and 1 ml of catalyst solution (= 5 ,moles of 'butylamido-2-indenyldimethylsilyl titanium dichloride) were placed in a 1.4 liter capacity steel autoclave. The autoclave was then filled with propylene up to a pressure of 2.0 bar. The temperature was then brought to 20°C. The polymerization was initiated by adding a solution of 18.5 mg (20 moles) of tri-phenylmethyltetrakis(penta-fluorophenyl) borate in 10 ml of toluene. Propylene was continuously added so that the pressure in the autoclave remained constant at 2.0 bar.
After a polymerization time of 50 mins at 20°C, the reaction was terminated with 500 ml of methanol, and the precipitated polymer was filtered off and dried for 20 hours at 60°C in vacuo. 68.9 g of atactic polypropylene were obtained.
Results of the GBC analysis: MW = 159000 g/mole, MW / Mn = 2.28. The '3C-NMR
spectroscopic investigation revealed the following composition: % mm = 19.1 (isotactic fraction); %(mr/rm) = 50.8 (atactic fraction); % rr = 30.0 (syndiotactic proportion); according to the DSC measurement, the polymer is completely amorphous. The enthalpy of melting was 0 J/g. A Tg value of -19°C was determined by the DSC method.

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Example 18 Copolymerization of ethylene and propylene 500 ml of hexane and 0.1 ml of TIBA were placed in a 1.4 1 capacity steel autoclave provided with a mechanical stirrer, manometer, temperature sensor, temperature control device, catalyst delivery tube and monomer metering devices for ethylene and propylene. 1 ml of the catalyst solution from Example 17 (= 5 .moles of 'butylamido-2-indenyldimethylsilyl titanium dichloride) was added. The internal temperature was adjusted with a thermostat to 20°C. 15 g of ethylene and 90 g of propylene were then added. The polymerization was initiated by adding a solution of 9.22 mg ( 10 moles) of triphenylmethyltetrakis(pentafluorophenyl) borate in 5 ml of toluene. Ethylene and propylene were continuously added in a semi-batch procedure in a mass ratio of 15:85 so that the internal pressure remained constant at 5 bar at 20°C. After 30 minutes of polymerization, the polymer was precipitated with methanol, isolated and dried for 20 hrs at 60°C in vacuo, 44 g of copolymers being obtained. The IR spectroscopic determination of the composition of the copolymer revealed an incorporation of 9.9 wt.% of ethylene and 90.1 wt.% of propylene.
According to the DSC measurement, the copolymer is completely amorphous. The enthalpy of melting was 0 J/g. A Tg of value of -28°C was determined by the DSC
method.
Example 19 Copolymerization of ethylene and propylene The polymerization of Example 18 was repeated, except that 21.3 g of propylene and 22.0 g of ethylene were placed in the autoclave and ethylene and propylene were continuously added in a mass ratio of 50:50. The polymerization time was 70 minutes. 57.2 g of an amorphous copolymer was obtained containing 49.9 wt.% of ethylene and 50.1 wt.% of propylene (IR spectroscopy). The measurement of the ' Le A 32 768-US

intrinsic viscosity gave a value of 2.59 dl/g. The determination of the Mooney value gave: ML (1+4) 125°C = 112.
Example 20 Copolymerization of ethylene and propylene The polymerization of Example 18 was repeated, except that 35.3 g of propylene and 14.9 g of ethylene were placed in the autoclave and ethylene and propylene were continuously added in a mass ratio of 30:70. The polymerization time was 120 minutes. 94 g of an amorphous copolymer was obtained containing 27.9 wt.% of ethylene and 72.1 wt.% of propylene (IR spectroscopy). The measurement of the intrinsic viscosity gave a value of 2.50 dl/g. The determination of the Mooney value gave: ML (1+4) 125°C = 107.
Example 21 Terpolymerization of ethylene, propylene and 5-ethylidene-2-norbornene (ENB) The polymerization of Example 20 was repeated, except that 45.6 g of propylene and 19.8 g of ethylene and 5 ml of ENB were placed in the autoclave and ethylene and propylene were continuously added in a mass ratio of 30:70. The polymerization time was 90 minutes. 80.2 g of an amorphous terpolymer containing 24.7 wt.% of ethylene, 71.6 wt.% of propylene and 3.81 wt.% of ENB was obtained (IR
spectroscopy). The measurement of the intrinsic viscosity gave a value of 2.56 dl/g.
The determination of the Mooney value gave: ML (1+4) 125°C = 123.
A Tg of value of -36°C was determined by the DSC method (melt enthalpy = 0 J/g).

' Le A 32 768-US

Example 22 Terpolymerization of ethylene, propylene and S-ethylidene and 2-norbornene (ENB) The polymerization of Example 20 was repeated, except that 21.3 g of propylene, 22.0 g of ethylene and S ml of ENB were placed in the autoklave and ethylene and propylene were continuously added in a mass ratio of 50:50. The polymerization time was 80 minutes. 67 g of an amorphons terpolymer containing 47.3 wt.-% of ethylene, 48.0 wt.% of propylene and 4.9 wt.% of ENB (IR spectroscopy) were obtained.
The measurement of the intrinsic viscosity gave a value of 2.26 dl/g. The determination of the Mooney value gave: ML(1+4) 125°C = 133.
A Tg of value of -51 °C was determined by the DSC method (melt enthalpy = 0 Jlg).
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.

Claims (13)

1. A process for preparing an amorphous, predominantly atactic polypropylene or amorphous propylene copolymer in a gaseous, liquid or slurry phase in the presence of an organo-metallic catalyst at a temperature of -20°C to +200°C and at a pressure of 1-50 bar, wherein said organometallic catalyst comprises a transition metal with an unsubstituted or substituted 2-indenyl as first ligand, said catalyst having the formula wherein A denotes a benzo system or a tetrahydrocyclohexyl system, Q as substituent of the optionally tetrahydrogenated

2-indenyl system denotes C1-C4-alkyl, C6-C14-aryl, C7-C10-aralkyl, C1-C4-alkoxy, C1-C4-alkylthio, phenoxy, phenylthio, di-C1-C4-alkylamino, C6-C14-aryl-C1-C4-alkylamino, di-C6-C14 arylamino, dibenzylamino, tri-C1-C4-alkylsilyl, di-C1-C4-alkylboranyl, phenyl-C1-C4-alkylboranyl, diphenylboranyl, di-C1-C4-alkylphosphoryl, diphenylphosphoryl or phenyl-C1-C4-alkylphosphoryl, m denotes an integer in the range from 0 to 6, M1 is a transition metal of the IV, V or VI
sub-groups of the Mendeleyev Periodic System of the Elements, X denotes an anion, n is a number from 0 to 4, which is determined by the valency and the bonding state of M1, Y denotes a bridge of -C(R1R2), -Si(R1R2)-, -Ge(R1R2)-, -C(R1R2)-C(R3R4)-, -C(R1R2)-Si(R3R4)- or -Si(R1R2)-Si(R3R4)-, wherein R1, R2, R3 and R4 denote, independently of one another, hydrogen, halogen, straight-chain or branched C1-C10-alkyl, C5-C8-cycloalkyl, C6-C14-aryl or C7-C10-aralkyl, and Z is a second ligand of an open-chain or cyclic, optionally anionic ~-system, -N(R5)-, -P(R6)-, ¦N(R5R7)-, ¦P(R6R8)-, -O-, -S-, ¦OR5- or ¦SR5-, the vertical line to the left of the element symbol N, P, O or S denoting an electron pair and the bond between Z and M1 having an ionic, covalent or coordinative character, and wherein R5, R6, R7 and R8 have, independently of one another, the same meanings as R1 to R4, and R5 and R7 may in addition denote -Si(R1R2R3) and R6 and R8 may in addition denote -Si(R1R2R3), -OR1, -SR1 or -N(R1R2).

2. A process according to claim 1, wherein Y denotes a bridge from the group consisting of -Si(R1R2)-, -Ge(R1R2)- and -Si(R1R2)-Si(R3R4)-.

3. A process according to claim 2, wherein Y denotes a bridge -Si(R1R2)-.

4. A process according to claim 1, 2 or 3, wherein M1 is a transition metal selected from the group consisting of Ti, Zr, Hf, V and Nb.

5. A process according to claim 4, wherein M1 is a transition metal selected from the group consisting of Ti, Zr and Hf.

6. A process according to claim 5, wherein M1 is a transition metal selected from the group consisting of Ti and Zr.

7. A process according to any one of claims 1 to 6, wherein a non-C2-symmetrical organometallic compound of a transition metal is used, wherein in formula (I) a second ligand Z' takes the place of Z and denotes a substituted or unsubstituted cyclopentadiene, substituted or unsubstituted 1-indene, unsubstituted 2-indene, substituted or unsubstituted fluorene, -N(R5)-, -P(R6)-, ¦N(R5-R7)-, ¦P(R6R8)-, -O-, -S-, ¦OR5- or ¦SR5.

8. A process according to any one of claims 1 to 6, wherein a non-C2-symmetrical organometallic compound of a transition metal is used, wherein in formula (I) a second ligand Z" takes the place of Z and denotes a substituted or unsubstituted 1-indenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted cyclopentadienyl, -N(R5)- or ¦N(R5R7)-, wherein, in formula (I), Y = -Si(R1R2)- and M1 - Ti or Zr.

9. A process according to claim 1, wherein tert-butyl-amido-2-indenyl-dimethylsilyl titanium dichloride is used as said organometallic compound.

10. A process according to any one of claims 1 to 9, wherein an ethylene-propylene copolymer is produced.

11. A predominantly amorphous, rubber-like propylene (co)polymer with a comonomer selected from C2-C10-.alpha.-olefins, arylalkenes, diolefins and cyclo(di)olefins.

12. A copolymer according to claim 11, wherein said copolymer is an amorphous, predominantly atactic poly-propylene (aPP).

13. A copolymer according to claim 11, having a molecular weight M w of > 100,000 g/mole.