Title of Invention	CARBON-BRIDGED CYCLOPENTADIENYL-FLUORENYL LIGANDS
Abstract	There is a process for preparing a catalyst component of general formula Ra2C (3,6-Rb2-Flu) (2-Rc-4-Rd-C5H2)MQ2 wherein Ra2C is a mono-carbon bridge and wherein either both Ra are hydrogen or one Ra is hydrogen and the other Ra is phenyl groups with or without substituents, such as herein described, or both Ra are phenyl groups with substituents, such as herein described, wherein Rb, Rc and Rd are each independently selected from H or alkyl having from 1 to 12 carbon atoms or aryl groups with or without substituents, such as herein described, with the restriction that they are not all simultaneously hydrogen, wherein M is a metal from Group 4 of the Periodic Table and wherein Q is halogen or alkyl having from 1 to 12 carbon atoms, and with the restriction that when Rc is alkyl group and one Ra is unsubstituted phenyl group, the other Ra is hydrogen, when Rc is alkyl group and one Ra is substituted phenyl group, the other Ra may be hydrogen or the same or another substituted phenyl group and the substituents are electron withdrawing groups, such as herein described, that when Rc is hydrogen, each Ra is independently selected form H or, with or without substituents, such as herein described, phenyl group, said process comprising: b) reaction by nucleophilic addition, in a solvent, of the group (Ra2C-2-Rc-4- Rd -fulvene) with the group [3,6-Rb2-Flu]- [M']+; b) hydrolysis and separation of the resulting ligand; c) deprotonation of the ligand of step b) with R'M" to prepare a di-anion ligand, wherein R' is an alkyl having from 1 to 6 carbon atoms and wherein M" is Li, Na or K; d) salt metathesis reaction in a solvent of the di-anion ligand of step c) with MQ4; e) isolation of the catalyst component.

Title of Invention

CARBON-BRIDGED CYCLOPENTADIENYL-FLUORENYL LIGANDS

Abstract

There is a process for preparing a catalyst component of general formula Ra2C (3,6-Rb2-Flu) (2-Rc-4-Rd-C5H2)MQ2 wherein Ra2C is a mono-carbon bridge and wherein either both Ra are hydrogen or one Ra is hydrogen and the other Ra is phenyl groups with or without substituents, such as herein described, or both Ra are phenyl groups with substituents, such as herein described, wherein Rb, Rc and Rd are each independently selected from H or alkyl having from 1 to 12 carbon atoms or aryl groups with or without substituents, such as herein described, with the restriction that they are not all simultaneously hydrogen, wherein M is a metal from Group 4 of the Periodic Table and wherein Q is halogen or alkyl having from 1 to 12 carbon atoms, and with the restriction that when Rc is alkyl group and one Ra is unsubstituted phenyl group, the other Ra is hydrogen, when Rc is alkyl group and one Ra is substituted phenyl group, the other Ra may be hydrogen or the same or another substituted phenyl group and the substituents are electron withdrawing groups, such as herein described, that when Rc is hydrogen, each Ra is independently selected form H or, with or without substituents, such as herein described, phenyl group, said process comprising: b) reaction by nucleophilic addition, in a solvent, of the group (Ra2C-2-Rc-4- Rd -fulvene) with the group [3,6-Rb2-Flu]- [M']+; b) hydrolysis and separation of the resulting ligand; c) deprotonation of the ligand of step b) with R'M" to prepare a di-anion ligand, wherein R' is an alkyl having from 1 to 6 carbon atoms and wherein M" is Li, Na or K; d) salt metathesis reaction in a solvent of the di-anion ligand of step c) with MQ4; e) isolation of the catalyst component.

Full Text	The present invention relates to new methods for the preparation of metallocene catalyst components based on carbon-bridged cyclopentadienyl-fluorenyl ligands. It is possible to develop catalyst systems that are able to produce different types of polymer such as isotactic, syndiotactic or atactic. It is however desirable that the selected catalyst produces predominantly an isotactic or syndiotactic polymer with very little atactic polymer. C2- or C1-symmetric metallocene catalysts are known to produce isotactic polyolefins. For example, C2 symmetric bis-indenyl type zirconocenes can produce high molecular weight high melting temperature isotactic polypropylene. The preparation of this metallocene catalyst is however costly and time-consuming. Most importantly, the final catalyst consists of a mixture of racemic and meso isomers in an often unfavourable ratio. The meso stereoisomer has to be separated to avoid the formation of atactic polypropylene during the polymerisation reaction. EP-A-0426644 relates to syndiotactic copolymers of olefins such as propylene obtainable using as a catalyst component isopropyl (fluorenyl)(cyciopentadienyl) zirconium dichloride. Syndiotacticity, as measured by the amount of syndiotactic pentads, rrrr was found to be 73-80%. EP 747406 relates to the polymerisation of an olefin monomer to form a syndiotactic/isotactic block polyolefin, particularly a block polypropylene. A component of the polymerisation catalyst was a 3-trimethyisily! cyclopentadienyl-9- fluorenyl zirconium or hafnium dichloride having an isopropylidene or diphenylmethylidene bridge. EP-A-577581 discloses the production of syndiotacfic poiypfopylenes using metaiiocene catalysts having fiuorenyl groups substituted in positions 2 and 7 and an unsubstituted cyclopentadienyl ring, EP-A-0419677 describes the production of syndiotactic polypropylene with an object to produce resin compositions having high stiffness when moulded. Metallcene catalysts such as isopropyl(cyclopentadienyl-1-fiuorenyl) zirconium dichloride were used in the production of the polypropylene. However the molecular weight, melting point and syndiolacticity of these products were relatively low. There is a need to develop new catalyst systems capable to provide polymers with improved properties and efficient methods for preparing them. It is an aim of the present invention to provide catalyst systems for the preparation of polymers having high molecular weight it is also an aim of the present invention to prepare polymers having a high melting temperature. it is another aim of the present invention to prepare impact copolymers having improved impact properties. It is a further aim of the present invention to prepare the catalyst systems capable to provide these improved polymers. Accordingly, the present invention provides a process for preparing a catalyst component of general formula Ra2C (3,6-Rb2-Flu) (2-Rc-4-Rd-C5H2) MQ2 wherein Ra2C is a mono-carbon bridge and wherein either both Ra arehydrogen or one Ra is hydrogen and the other Ra is phenyl groups with or without substituents, such as herein described, or both Ra are phenyl groups with substituents, such as herein described, wherein Rb, Rc and Rd are each independently selected from H or alky having from 1 to 12 carbon atoms or aryl groups with or without substituents, such as herein described, with the restriction that they are not all simultaneously hydrogen, wherein M is a metal from Group 4 of the Periodic Table and wherein Q is halogen or alkyl having from 1 to 12 carbon atoms, and with the restriction that when Rc is alkyl group and one Ra is unsubstituted phenyl group, the other Ra is hydrogen, when Rc is alkyl group and one Ra is substituted phenyl group, the other Ra may be hydrogen or the same or another substituted phenyl group and the substituents are electron withdrawing groups, such as herein described, that when Rc is hydrogen, each Ra is independently selected form H or, with or without substituents, such as herein described, phenyl group, said process comprising: a) reaction by nucleophilic addition, in a solvent, of the group (Ra2C-2-Rc-4- Rd -fulvene) with the group [3,6-Rb2-Flu]- [M]+; b) hydrolysis and separation of the resulting ligand; c) deprotonation of the Iigand of step b) with R'M" to prepare a di-anion iigand, wherein R' is an alkyl having from 1 to 6 carbon atoms and wherein M" is Li, Na or K; d) salt metathesis reaction in a solvent of the di-anion Iigand of step c) with MQ4; e) isolation of the catalyst component. In a preferred embodiment according to the present invention in the bridge Ra2C, one Ra is unsubstituted phenyl and the other Ra is H. In another preferred embodiment, both Ra in the bridge are substituted phenyl groups. The substituents on the phenyl groups preferably are electron withdrawing groups that can be selected from halogen, more preferably F or CI, or from CX3 wherein X is a halogen, more preferably F, preferably F or from NO2. The substituents on the phenyl groups can be located at position 4 in the case of a single substituent, or at positions 3 and 5 for 2 if there are 2 substituents. Preferably both phenyls have the same substitution pattern. Possible substituents to the "aryl groups" are "halogen or CX3", wherein X is halogenf or C1-C6 alkyl. Throughout this description, the positions are labelled as represented below. Preferably, both Rb are the same and are alkyl having from 1 to 6 carbon atoms, more preferably they both are tert-butyi. Preferably Rc is H or methyl. Preferably Rd is alkyl having from 1 to 6 carbon atoms, more preferably, it is tert- butyl. Preferably M is Zr, Hf or Ti, more preferably, it is Zr. Preferably Q is halogen or methyl, more preferably it is chlorine. Preferably, Ma is Li. The solvent of steps a) and d) may be the same or different and are hydrocarbon, preferably selected from pentane, toluene, tetrahydrofuran (THF) or diethyl ether (Et2O). Preferably they are the same and it is H2O. Without Wishing to be bound by a theory, it is believed Et2O stabilises a transition state of the nucleophilic addition reaction including bulky constrained reagents. The reaction of step a) is carried out at a temperature of from 0 to 60 °C, preferably at room temperature for a period of time of from 6 to 24 hours, preferably of about 12 hours. Any activating agent having an ionising action known in the art may be used for activating the metallocene component- For example, it can be selected from aluminium-containing or boron-containing compounds. The aluminium-containing compounds comprise aluminoxane, alkyl aluminium and/or Lewis acid. The aluminoxanes are preferred and may comprise oligomeric linear and/or cyclic alkyl aluminoxanes represented by the formula: wherein n is 1-40, preferably 10-20, m is 3-40, preferably 3-20 and R is a C1-C8 alkyl group and preferably methyl. Suitable boron-containing activating agents that can be used comprise a triphenylcarbenium boronate such as tetrakis-pentafluorophenyl-borato- triphenylcarbenium as described in EP-A-0427696, or those of the general formula [L'-H] + [B Ar1 Ar2 X3 X4]- as described in EP-A-0277004 (page 6, line 30 to page 7, line 7). The catalyst system can also be supported. The support if present can be a porous mineral oxide, advantageously selected from silica, alumina and mixtures thereof. Preferably it is silica. Alternatively, an activating support can be used. The catalyst system of the present invention can be used in the polymerisation of ethylene and alpha-olefins. It is preferably used to prepare highly isotactic propylene homopolymers having a high weight average molecular weight of at least 500 kDa, preferably at least 700 kDa, a high melting temperature of more than 150 °C, preferably Of more than 160 °C, and an mmmm of more than 95. It can also be used to prepare ethylene-propylene rubber (EPR) having an ethylene content of from 8 to 15 wt%, a high weight average moiecuiar weight of at least 500 kDa, preferably at least 700 kDa, and a melt flow index MFI of from 2 to 10 dg/min. The melt flow index is measured following the method of standard test ASTM D 1238 under a load of 2.16 kg and at a temperature of 230 oC. The EPR obtained in the present invention is characterised by excellent impact properties. It can be used in all applications that require elastomers with excellent thermoplastic properties. List of Figures. Figure 1 represents the reaction scheme for the preparation of complex H2C(3,6- tBu2Fiu)(3-tBu-5-Me-Cp)ZrCi2(3). Figure 2 represents the 1H NMR spectrum of ligand 3,6-di tert-buiyl-9-[(3-tert-butyl-5- meihyicyciopenia-1 ,4-dien-1 -yl)methyl]-9H-fiuorene (2). Figure 3 represents the 1H NMR spectrum of complex H2C(3,6-tBu2Flu)(3-tBu-5-Me- Cp)ZrCI2(3). Figure 4 represents the reaction scheme for the preparation of complex PhHC(3,6- tBu2Flu)(3-tBu-5-Me-Cp)ZrCI2 (6). Figure 5 represents the 1H NMR spectrum of 6-phenyl-2-methyl-4-tert-butyI-fulvene (4). Figure 6 represents the 1H NMR spectrum of ligand 3,6-Di-tert-butyl-9-[(4-tert-butyl- 2-methyl-cyclopenta-1,4-dienyl)-phenyl-ethyl]-9H-fluorene (5). Figure 7 represents the 1HNMR spectrum of complex PhHC(3,6-tBu2Flu)(3-tBu-5-Me- Cp)ZrCI2 (6). Figure 8 represents the reaction scheme for the preparation of complex Ph2C(3,6- tBu2-Flu)(3-tBu-Cp)ZrCI2 (9). Figure 9 represents the reaction scheme for the preparation of complex (p-CI- Ph)2C(3,6-tBu2Flu)(3-tBu-5-Me-Cp)ZrCI2(17). Figure 10 represents the reaction scheme for the preparation of ligand 3,6-di-tert- butyl-9-{(4-tert-butyI-2-methylcyclopenta-1,4-dien-1-yl)[bis(4-fluorophenyl)]methyl}- 9H-fluorene (19). Figure 11 represents the reaction scheme for the preparation of ligand 9-[bis[3,5- bis(trifluoromethyl)pheny\|](4-tert-butyl-2-methylcyclopenta-1,4-dien-1-yl)methyl3-3,6- di-tert-butyl-9H-fluorene (21). Figure 12 represents the reaction scheme for the preparation of ligand 9-[[3,5- bis(trifluoromethyl)phenyl](4-tert-butyl-2-methylcyclopenta-1,4-dien-1-yl)methyl]-3,6- di-tert-butyl-9H-fluorene (23). Examples. All experiments were performed under purified argon atmosphere using standard Schlenk techniques or in a glovebox. Solvents were distilled from Na/benzophenone (tetrahydrofuran (THF), diethyl ether (Et2O)) and Na/K alloy (toluene, pentane) under nitrogen, they were thoroughly degassed and stored under nitrogen. Deuterated solvents (benzene-d6, toluene-d8, THF-d8; >99.5% D, Deutero GmbH) were vacuum- transferred from Na/K alloy into storage tubes. Chloroform-d1 and CD2CI2 were kept over calcium hydride and vacuum-transferred before use. The precursors 3,6,6'- trimethyl-fulvene, 2-methyl-4-tert-butyl-cyclopentadiene (mixture of isomers) and 1- methyl-3-tert-butyl-cyclopentadienyl lithium were prepared according to known procedures and characterised by 1H NMR spectroscopy. 1-tert-butyl-cyclopentadiene (mixture of isomers) was prepared according to a procedure described in Moore and Jean King (Moore W.R. and Jean King B., J. Org. Chem., 36,1882,1971). Synthesis of complex H2C(3,6-tBu2Flu)(3-tBu-5-Me-Cp)ZrCI2 (3). The scheme is represented in figure 1. a) Synthesis of 3,6-di-tert-butyl-9-[(3-tert-butyl-5-methylcyclopenta-1,4-dien-1- vnmethyl]-9H-fluorene (2). To a solution of 3.2 g (16.73 mmol) of 6-dimethylamino-2-methyl-4-tert-butyl-fulvene in 50 ml. of THF were added, at room temperature, 50 mL of a solution of 3,6-di-tert- butyl-fluorenyl-lithium prepared from 4.65 g (16.70 mmol) of 3,6-di-tert-butyl-fiuorene and 6.70 mL (16.70 mmol) of a 2.5 M solution of n-butyl-lithium. The reaction mixture was stirred for 12 h at room temperature. Then 1.17 g (30.79 mmol) of LiAIH4 were added and the resulting mixture was refluxed for another 12 h and then carefully quenched with 50 mL of a saturated solution of NH4CI diluted with 100 mL of diethyl ether. The organic layer was separated, washed twice with 200 mL of water and dried over CaCI2. All the volatiles were removed in vacuum. The crude yellow product was purified by column chromatography over silica gel to give 4.27 g (10.02 mmol) of final product 2 with a yield of 60 % yield. This product was a 1:1 mixture of double bond isomers in the cyclopentadienyl ring. 1H NMR (CDCI3, 300 MHz, 25 °C) spectrum is presented in Figure 2 and is characterised as follows : 8 7.78 (s, 4H, Flu), 7.40-7.10 (m, 8H, Flu), 7.08 (dd, 1H, Flu), 6.18 (s, 1H, Cp), 5.97 (d, 1H, Cp), 4.00 (q, 2H, 3J = 14.7 Hz, 9-Flu), 3.00 (m, 4H, CH2, Cp), 2.70 (m, 4H, CH2), 1.73, 1.66 (s, 3H, CH3), 1.42 (s, 36H, CCH3-Flu), 1.21 (s, 18H, CCH3-FIU). Anal. Calcd for C32H42: C, 90.08; H, 9.92. Found: C, 91.01; H, 9.99. b) Synthesis of the complex H9C(3,6-tBu2Flu)(3-tBu-5-Me-Cp)ZrCI2 (3). To a solution of 1.67 g (3.91 mmol) 6-dimethylamino-2-methyl-4-tert-butyl-fulvene (1) in 40 ml of Et2O were added 3.10 ml (7.82 mmol) of a 2.5 M solution of butyl-lithium in hexane at 0 °C. The reaction mixture was stirred for 4 h and the solvent was evaporated under reduced pressure. Then in glovebox 0.91 g (3.90 mmol) of anhydrous ZrCI4 were added followed by the addition of 50 mL of pentane. The resulting pink reaction mixture was stirred at room temperature overnight The reaction mixture was filtered off and the filtrate was evaporated in vacuum. A portion of about 30 mL of hexane was added and the resulting clear solution was kept at -30 °C overnight to give a pink microcrystalline powder precipitate of complex 3. A second batch of 1.48 g (2.52 mmol) of product 3 was obtained from the mother liqueur upon cooling with a yield of 64 %. Crystals suitable for X-ray diffraction were obtained by slow concentration from a 3:7 CH2CI2/hexane mixture. 1H NMR (CD2CI2, 300 MHz, 25 °C) spectrum is presented in Figure 3 and is characterised as follows : δ 8.01 (s, 1H, Flu), 7.97 (s, 1H, Flu), 7.52 (s, 1H, Flu), 7.40 (m, 2H, Flu), 7.37 (m, 1H, Flu), 6.02 (d, 1H, 4J = 2,8 Hz, Cp), 5.52 (d, 1H, 4J = 2,8 Hz, Cp), 4.74 (m, 2H, CH2), 2.16 (s, 3H, CH3), 1.44 (s, 9H, CCH3-FIU), 1.43 (s, 9H, CCH3-Flu), 1.05 (s, 9H, CCH3-Flu). 13C NMR (CD2CI2, 75 MHz, 25 °C): 8 150.1,150.0,146.4,127.9, 127.6,124.8, 124.1,124.0,123.3,121.8,120.7,120.6,120.2,119.7,118.2,102.4, 97.0, 70.3, 35.6, 33.3, 32.2, 32.1, 32.0, 30.0, 22.5 (CH2), 16.1. Anal. Calcd for C32H40Cl2Zr : C, 65.50; H, 6.87; CI, 12.08. (Molecular mass Mr = 586.79 kg/mol) Found: C, 66.12; H, 6.99. Synthesis of the complex Ph(H)C(3.6-tBu2Flu)(2-Me-4-tBu-Cp)ZrCI2 (6). The scheme is represented in Figure 4. a) Synthesis of 6-Dhenyl-2-methyl-4-tert-butyl-fulvene (4). To a solution of 1.94 g (14.24 mmol) of 1-methyl-3-tert-butyl-cyclopentadiene (mixture of isomers) in 50 mL of diethyl ether were added 5.7 mL (14.24 mmol) of a 2.5 M solution of butyllithium in hexane at 0 °C. The reaction mixture was stirred for 2 hours and a solution of 1.44 mL (14.24 mmol) of benzaldehide in 30 mL of ether was added drop-wise. The reaction mixture became orange. After 2 hours, 50 mL of a concentrated solution of NH4CI was added slowly. This mixture was stirred overnight. The organic layer was separated, dried over MgSO4 and all the volatiles were removed in vacuum. The orange residue was recrystallised from methanol at - 30 °C to give 1.0 g (4.46 mmol) of compound (1) with a yield of 31 %. 1H NMR (CDCl3, 300 MHz, 25 °C) spectrum is presented in Figure 5 and is characterised as follows: δ 7.57 (m, 2H, Ph), 7.40 (m, 3H, Ph), 7.01 (s, 1H, =CHPh), 6.24 (t, 1H, CH), 6.14 (d, 1H, CH), 2.15 (s, 3H, CH3), 1.19 (s, 9H, CCH3). 13C NMR (CD2CI2, 75 MHz, 25 °C): 8160.4,145.9,137.4,135.5,131.9,129.5, 128.4,128.2,128.0,127.2,125.5,110.5, 32.1,29.5,12.6. b) Synthesis of 3,6-Di-tert-butyl-9-[(4-tert-butyl-2-methyl-cyclopenta-1,4-dienyI)- phenyl-ethyl]-9H-fluorene (5). To a solution of 1,75 g (7.80 mmol) of compound (1) in 20 mL of THF were added, at room temperature, 30 mL of a solution of 3,6-di-tert-bulyl-fluorenyl-lithium prepared by reacting 1.95 g (7.00 mmol) of 3,6-di-tert-butyl-fluorene with 2.80 mL (7.00 mmol) of a 2.5 M solution of n-butyl-lithium. The reaction mixture was stirred for 4 h at ambient temperature (about 25 °C) and then quenched with 50 mL of a saturated solution of NH4CI and diluted with 50 mL of diethyl ether. The organic layer was separated, washed twice with 200 mL of water and dried over CaCI2. All the volatiles were removed in vacuum and the residue was dissolved in hot MeOH. The solution was cooled to -30 °C and a white precipitate formed. This latter was filtered and washed with cold methanol (-30 °C) and dried in vacuum overnight to give 2.30 g (4.57 mmol) of final product (2) with a yield of 65 %. It contains about 20 % of isomer 3,6-di-tert-butyl-9-[(4-tert-butyl-2-methylcyclopenta-1,3-dien-1-yl) (phenyl) methyfJ-9H-fluorene. 1H NMR (CDCI3,300 MHz, 25 °C) spectrum is presented in Figure 6 and is characterised as follows: δ 7.70 (dd, 2H, Flu), 7.35 (m, 5H, Ph), 7.08 (dd, 1H, Flu), 6.95 (dd, 1H, Flu), 6.83 (d, 1H, Flu), 6.29 (t, 2H, Flu), 4.48 (d, 1H, 3J= 10.6 Hz, CHPh), 3.68 (d, 1H, 3J= 10.6 Hz, 9-Flu), 2.79 (s, 2H, CH2, Cp), 1.60 (s, 3H, CH3), 1.37 (s, 9H, CCH3-FIu), 1.33 (s, 9H, CCH3-Flu), 1.14 (s, 9H, CCH3-Flu). 13C NMR (CD2CI2, 75 MHz, 25 °C): 5 155.6,150.0,149.9,144.2,143.9,143.6, 141.4,141.3,139.9,139.8,134.6,128.9,128.7,128.6,126.4,125.6,125.3,124.7, 123.5,123.4,115.9,115.8, 51.0, 50.9,49.4, 44.0, 34.9, 33.2, 31.8, 31.1, 13.4. c) Synthesis of the complex Ph(H)C(3,6-tBu2Flu)(2-Me-4-tBu-Cp)ZrCl2 (6). To a solution of 1.025 g (2.04 mmol) of compound 2 in 40 ml of Et2O were added 1.67 mL (4.08 mmol) of a 2.5 M solution of butyl-lithium in hexane at 0 °C. The reaction mixture was stirred for 4 h and then 0.475 g (2.04 mmol) of anhydrous ZrCU were added in a glovebox. The resulting pink reaction mixture was stirred at room temperature overnight. The solvent was then evaporated in vacuum and 40 mL of hexane were condensed under reduced pressure. The resulting mixture was filtered off and the filtrate was evaporated in vacuum to a give 1.18 g (1.78 mmol) of a pink powder of crude complex (3) with a yield of 88 %. A new quantity of 20 mL of hexane was added to the pink residue. After a period of time of from 1 to 2 hours, a pink precipitate formed. It was isolated by decantation, washed with 10 mL of cold hexane and dried in vacuum to yield 0.53 g (8.80 mmol) of di-chloro-zirconocene (3) with a yield of 40 %. Crystals suitable for X-ray measurements were obtained by slow concentration from a 1:9 CH2CI2/hexane mixture. 1H NMR (CD2CI2, 300 MHz, 25 °C) spectrum is presented in Figure 7 and is characterised as follows: 8 8.03 (dd, 2H, Flu), 7.78 (d, 2H), 7.58 (d, 1H), 7.48 (m, 2H), 7.43 (m, 2H), 7.08 (dd, 1H, Flu), 6.57 (d, 1H, Flu), 6.50 (s, 1H, Cp), 6.12 (d, 1H, 4J = 2,6 Hz, Cp), 5.57 (d, 1H, 4J = 2,6 Hz, CHPh), 2.21 (s, 3H, CH3), 1.45 (s, 9H, CCH3-FIU), 1.38 (s, 9H, CCH3-Flu), 1.05 (s, 9H, CCH3-Flu). 13C NMR (CD2CI2, 75 MHz, 25 °C) (Fig. 4): 5 150.2, 150.0,147.1,140.1,129.2, 128.9, 128.6, 128.4,128.2, 127.6,126.7, 125.9, 125.3,124.8,122.8,122.5,121.5, 120.0, 119.5, 119.3,116.9,103.2,100.9, 74.6, 40.2, 35.5, 35.4, 33.2, 32.0, 29.7, 15.8. Anal. Calcd for C38H44Cl2Zr: C, 68.85; H, 6.69; CI, 10.70. (Mr = 662.885 kg/mol); Found: C, 69.01; H, 7.37. Synthesis of complex Ph2C(3,6-tBu2-Flu)(3-tBu-C5H3)ZrCl2 (9). The scheme is represented in Figure 8. a) Synthesis of Ph2C(3,6-tBu2-FluH)(3-tBu-C5H4) (8). The reaction of sterically hindered stabilized 6,6'-diphenyl fulvenes with fluorenyl- anion is known to proceed sluggishly and requires prolonged and significant heating. The reaction between 6,6'-diphenyl-3-tert-butyl-fulvene (7) and fluorenyl-anion appeared to depend upon the nature of the solvent Diethyl ether gave the best results: the reaction proceeded over 5-7 days at a temperature of 60 to 70 °C to give the desired product (8) with a yield of 21 %. b) Synthesis of complex Ph2C(3,6-tBuyFlu)(3-tBu-C5H3)ZrCl2 (9). Salt metathesis reaction between ligand (8) dianion generated in situ and ZrCl4 was carried out. The reaction proceeded at room temperature in pentane with concomitant precipitation of LiCI. After a usual workup the reaction mixture was kept as a hexane solution for one month at room temperature to obtain red micro-crystals of complex (9) with a yield of 46 %. 1H and 13C NMR spectroscopy of complex (9) displayed a dissymmetric structure in solution similar to one described for complexes (3) and (6). Synthesis of (p-CI-Ph)2C(3,6-di-tert-butyl-9fluorenyl)(2-Me-4-tert-butyl- cvclopentadienyl) zirconium dichloride (17). The scheme is represented in Figure 9. a) Synthesis of 6,6'-bis(4-chloro-ohenyl)- 4-tert-butyl-2-methyl-fulvene (14). To a solution of 2.27 g (16.66 mmol) of a mixture of isomers of 1-methyl-3-tert-butyl- cyclopentadiene in 150 mL of tetrahydrofuran, were added 6.67 mL (16.66 mmol) of a d 2.5 M solution of butyllithium in hexane, at 0 °C. The reaction mixture was stirred for 2 hours and 4.18 g (16.66 mmol) of a solution of 4,4'-dichlorobenzophenone in 50 mL of THF were added dropwise. The reaction mixture turned orange. After 4 hours, 50 mL of a concentrated solution of NH4CI were added slowly. The mixture was stirred overnight. The organic layer was separated, dried over MgSO4 and all the volatiles were removed in vacuum. The orange residue was recrystallized from hot methanol at 25 °C to give 3.7 g (10.02 mmol) of 6,6'-bis(4-chloro-phenyl)-2-methyl-4- tert-butyl-fulvene with a yield of 60 % yield. 1H NMR (CDCI3l 400 MHz, 25 °C) is characterised as follows: δ 7.32 (m, 4H, Ph), 7.18 (m, 4H, Ph), 6.37 (s, 1H, Cp), 5.66 (s, 1H, Cp), 1.53 (s, 3H, CH3), 1.17 (s, 9H, CCH3). Anal. Calcd for C23H22CI2: C, 74.80; H, 7.00. Found: C, 74.85; H, 7.10. b) Synthesis of 3.6-di-tert-butyl-9-((4-tert-butyl-2-methylcyclopenta-1,4-dien-1- yl)[bis(4-chlorophenyl)]methyl}-9H-fluorene (15). To a solution of 1.33 g (3.60 mmol) of 6,6'-bis(4-chloro-phenyl)-2-methyl-4-tert-butyl- fulvene in 30 mL of Et2O were added, at room temperature, 30 mL of a solution of 3,6-di-tert-butyl-fluorenyl-lithium in Et2O, prepared from 1.0 g (3.59 mmol) of 3,6-di- tert-butyl-fluorene and 1.44 mL (3.59 mmol) of a 2.5 M solution of n-butyl-lithium in hexane. The reaction mixture was stirred for 5 days upon reflux and then quenched with 50 mL of a saturated solution of NH4CI, diluted with 50 mL of diethyl ether. The organic layer was separated, washed twice with 200 mL of water and dried over CaCl2. All the volatiles were removed in vacuum. The residue was washed with MeOH then with cold pentane at a temperature of -30 °C on a filter and dried in vacuum overnight to give 1.4 g (2.16 mmol) of final product with a yield of 60 %. Mass spectrum MS-ESI: m/z 645.7 , 370.3 ,277.4. 1H NMR (THF-d8, 300 MHz, 90 °C) is characterised as follows: 8 7.53 (br s, 2H, Flu), 7.40-6.80 (br m, 14H, Ph and Flu), 6.20 (br s, 1H, Cp), 5.64 (s, 1H, 9-Flu), 2.78 (s, 2H, CH2, Cp), 1.36 (s, 3H, CH3), 1.32 (s, 18H, CCH3-Flu), 1.09 (s, 9H, CCH3-Flu). 13C NMR (THF-d8, 75 MHz, 90 °C): 5 151.0, 150.1, 149.8, 144.7, 144.3, 143.5, 143.3, 143.2, 141.8, 135.0, 133.7, 133.1, 131.9, 131.5, 130.1, 129.6, 128.9, 127.1, 126.5, 125.3, 123.9, 116.5, 116.3, 116.2, 57.1, 55.4, 41.3, 35.2, 32.5, 31.9, 31.8, 28.9, 28.7, 28.3. Anal. Calcd for C44H48CI2: C, 81.58; H, 7.47. Found: C, 82.04; H, 8.55. The zirconocene (17) was then obtained by reaction with anhydrous ZrCl4 following the same scheme as that depicted for preparing complex (3) or complex (6). Alternatively, each phenyl group in the bi-phenyl bridge can be substituted by fluorine at position as shown on figure 10 or by two CF3 respectively at positions 3 and 5 as shown on figure 11. Synthesis of (3,5-bis(trifluoromethyl)-phenyl)CH(3,6-di-tert-butyl-9fluorenyl)(2- Me-4-tert-butyl-cyclopentadienyl) zirconium dichloride (24). a) Synthesis of 6-(3,5-bis(trifluoromethyl)-henyl)-3-tert-butyl-5-methyl-fulvene (22). To a solution of 2.81 g, (20.63 mmol) of a mixture of isomers of 1-metbyl-3-tert-butyl- cyclopentadienyl in 150 mL of diethyl ether, were added 8.20 mL (20.63 mmol) of a 2.5 M solution of butyilithium in hexane, at 0 °C. The reaction mixture was stirred for 2 hours and a solution of 5.0 g (20.65 mmol) of 3,5-bis(trifluoromethyl)benzaldehide in 50 mL of ether was added dropwise. The reaction mixture turned red. After 2 hours, 50 mL of a concentrated solution of NH4CI was added slowly. This mixture was stirred overnight. The organic layer was separated, dried over MgSO4 and all the volatiles were removed in vacuum. The orange residue was recrystallized from methanol at -30 °C to give 2.60 g (7.22 mmol) of compound 22 with a yield of 35 %. 1H NMR (CDCI3, 300 MHz, 25 °C) is characterised as follows: δ 7.92 (s, 2H, Ph), 7.79 (s, 1H, Ph), 6.95 (s, 1H, =CHPh), 6.25 (t, 1H, CH), 5.92 (d, 1H, CH), 2.11 (s, 3H, CH3), 1.15 (s, 9H, CCH3). 19F NMR (CDCI3, 282 MHz, 25 °C): δ -62.6. Anal. Calcd for C34H32F2: C, 62.98; H, 5.56. Found: C, 63.67; H, 5.98. b) Synthesis of 9-[[3,5-bis(trifluoromethyl)phenyl](4-tert-butyl-2-methylcyclopenta- 1,4-dien-1-yl)methyl]-3,6-di-tert-butyl-9H-fluorene (23). The scheme for preparing component (23) is represented in Figure 12. To a solution of 2.60 g (7.21 mmol) of compound 22 in 25 mL of THF, were added, at room temperature, 30 mL of a solution of 3,6-di-tert-butyl-fluorenyl-lithium prepared from 2.00 g (7.20 mmol) of 3,6-di-tert-butyl-fluorene and 2.90 mL (7.21 mmol). of a 2.5 M solution of n-butyl-lithium. The reaction mixture was stirred for 4 h at room temperature and then quenched with 50 mL of a saturated solution of NH4CI diluted with 50 mL of diethyl ether. The organic layer was separated, washed twice with 200 mL of water and dried over CaCl2. All the volatiles were removed in vacuum. The residue was purified by column chromatography over silica gel using hexane as an eluent to give 0.2 g (0.31 mmol) of final compound 23 as a mixture of two isomers in relative amounts of 2:3 with a yield of 4 %. 1H NMR (CDCI3, 300 MHz, 25 °C) is characterised as follows: δ 7.70 (m, 3H, Ph), 7.20-6.30 (m, 6H, Flu), 6.20 (s, 1H, Cp), 5.91 (s, 1H, Cp), 4.48 (m, 1H, CHPh), 3.95 (m, 1H, 9-Flu), 3.19-2.73 (m, 2H, CH2, Cp), 1.59-1.52 (s, 3H, CH3), 1.36-1.33 (s, 18H, CCH3-Flu), 1.16-1.14 (s, 9H, CCH3-Flu). 19F NMR (CDCI3, 282 MHz, 25 °C): 8 -62.41, -62.45. Anal. Calcd for C40H44F6: C, 75.21; H, 6.94. Found: C, 76.14; H, 7.01. The zirconocene (24) was then prepared following the method used to prepare components (3) and (6). The catalyst components synthetised here-above were tested in the homo- or co- polymerisation of propylene. They were activated with methylaluminoxan (MAO) and optionally deposited on a silica support: they produced highly isotactic homopolymers of propylene or ethylene-propylene rubber (EPR) having excellent impact properties. The polymerisation conditions and results are displayed in Table I for heterogeneous polymerisation and in Table II for homogeneous polymerisation. All resins produced with the new catalyst system according to the present invention had very high molecular weights and melting temperature. Additional examples carried out on the copolymerisation of ethylene with propylene led to ethylene-propylene rubber having high viscosity, high molecular weight and melt flow rate smaller than 10 dg/min and thus excellent impact properties. With prior art catalyst systems, the molecular weight of the EPR was very low with a very low viscosity leading to bad impact properties. WE CLAIM: 1. A process for preparing a catalyst component of general formula Ra2C (3,6-Rb2-Flu) (2-Rc-4-Rd-C5H2)MQ2 wherein Ra2C is a mono-carbon bridge and wherein either both Ra are hydrogen or one Ra is hydrogen and the other Ra is phenyl groups with or without substituents, such as herein described, or both Ra are phenyl groups with substituents, such as herein described, wherein Rb, Rc and Rd are each independently selected from H or alkyl having from 1 to 12 carbon atoms or aryl groups with or without substituents, such as herein described, with the restriction that they are not all simultaneously hydrogen, wherein M is a metal from Group 4 of the Periodic Table and wherein Q is halogen or alkyl having from 1 to 12 carbon atoms, and with the restriction that when Rc is alkyl group and one Ra is unsubstituted phenyl group, the other Ra is hydrogen, when Rc is alkyl group and one Ra is substituted phenyl group, the other Ra may be hydrogen or the same or another substituted phenyl group and the substituents are electron withdrawing groups, such as herein described, that when Rc is hydrogen, each Ra is independently selected form H or, with or without substituents, such as herein described, phenyl group, said process comprising: a) reaction by nucleophiiic addition, in a solvent, of the group (Ra2C-2-Rc-4- Rd -fulvene) with the group [3,6-Rb2-Flu]- [M']+; b) hydrolysis and separation of the resulting ligand; c) deprotonation of the ligand of step b) with R'M" to prepare a di-anion ligand, wherein R' is an alkyl having from 1 to 6 carbon atoms and wherein M" is Li, Na or K; d) salt metathesis reaction in a solvent of the di-anion ligand of step c) with MQ4; e) isolation of the catalyst component. 2. The process as claimed in claim 1, wherein the substituents on the phenyl groups, if present, are at position 4 for a single substituent or at positions 3 and 5 for 2 substituents. 3. The process as claimed in claim 1 or claim 2, wherein both Rb are the same and are tert- butyl. 4. The process as claimed in any one of preceding claims, wherein Rc is methyl at position 2 and Rd is tert-butyl at position 4. 5. The process as claimed in any one of the preceding claims, wherein the solvent of step a) is Et2O. 6. The process as claimed in claim 5, wherein the solvent in step d) is also Et2O. 7. The process as claimed in any one of the preceding claims wherein M" is Li. 8. Process for preparing ethylene-propylene rubber, employing the metallocene catalyst component obtained by the process as claimed in any of claims 1 to 7, in combination with an activating agent, such as herein described, the ethylene-propylene rubber, so prepared, having an ethylene content of from 8 to 15 wt%, a weight average molecular weight of at least 500 kDa and excellent impact properties. 9. The process for preparing isotactic polypropylene, employing the metallocene catalyst component obtained by the process as claimed in any of claims 1 to 7, in combination with an activating agent, such as herein described, said isotactic polypropylene, so prepared, having a weight average molecular weight of more than 500 kDa, a melting temperature of more than 150 °C and an mmmm of more than 95. ABSTRACT CARBON-BRIDGED CYCLOPENTADIENYL-FLUORENYL LIGANDS There is a process for preparing a catalyst component of general formula Ra2C (3,6-Rb2-Flu) (2-Rc-4-Rd-C5H2)MQ2 wherein Ra2C is a mono-carbon bridge and wherein either both Ra are hydrogen or one Ra is hydrogen and the other Ra is phenyl groups with or without substituents, such as herein described, or both Ra are phenyl groups with substituents, such as herein described, wherein Rb, Rc and Rd are each independently selected from H or alkyl having from 1 to 12 carbon atoms or aryl groups with or without substituents, such as herein described, with the restriction that they are not all simultaneously hydrogen, wherein M is a metal from Group 4 of the Periodic Table and wherein Q is halogen or alkyl having from 1 to 12 carbon atoms, and with the restriction that when Rc is alkyl group and one Ra is unsubstituted phenyl group, the other Ra is hydrogen, when Rc is alkyl group and one Ra is substituted phenyl group, the other Ra may be hydrogen or the same or another substituted phenyl group and the substituents are electron withdrawing groups, such as herein described, that when Rc is hydrogen, each Ra is independently selected form H or, with or without substituents, such as herein described, phenyl group, said process comprising: b) reaction by nucleophilic addition, in a solvent, of the group (Ra2C-2-Rc-4- Rd -fulvene) with the group [3,6-Rb2-Flu]- [M']+; b) hydrolysis and separation of the resulting ligand; c) deprotonation of the ligand of step b) with R'M" to prepare a di-anion ligand, wherein R' is an alkyl having from 1 to 6 carbon atoms and wherein M" is Li, Na or K; d) salt metathesis reaction in a solvent of the di-anion ligand of step c) with MQ4; e) isolation of the catalyst component.

Full Text

The present invention relates to new methods for the preparation of metallocene
catalyst components based on carbon-bridged cyclopentadienyl-fluorenyl ligands.
It is possible to develop catalyst systems that are able to produce different types of
polymer such as isotactic, syndiotactic or atactic. It is however desirable that the
selected catalyst produces predominantly an isotactic or syndiotactic polymer with
very little atactic polymer. C2- or C1-symmetric metallocene catalysts are known to
produce isotactic polyolefins. For example, C2 symmetric bis-indenyl type
zirconocenes can produce high molecular weight high melting temperature isotactic
polypropylene. The preparation of this metallocene catalyst is however costly and
time-consuming. Most importantly, the final catalyst consists of a mixture of racemic
and meso isomers in an often unfavourable ratio. The meso stereoisomer has to be
separated to avoid the formation of atactic polypropylene during the polymerisation
reaction.
EP-A-0426644 relates to syndiotactic copolymers of olefins such as propylene
obtainable using as a catalyst component isopropyl (fluorenyl)(cyciopentadienyl)
zirconium dichloride. Syndiotacticity, as measured by the amount of syndiotactic
pentads, rrrr was found to be 73-80%.
EP 747406 relates to the polymerisation of an olefin monomer to form a
syndiotactic/isotactic block polyolefin, particularly a block polypropylene. A
component of the polymerisation catalyst was a 3-trimethyisily! cyclopentadienyl-9-
fluorenyl zirconium or hafnium dichloride having an isopropylidene or
diphenylmethylidene bridge.

EP-A-577581 discloses the production of syndiotacfic poiypfopylenes using
metaiiocene catalysts having fiuorenyl groups substituted in positions 2 and 7 and an
unsubstituted cyclopentadienyl ring,
EP-A-0419677 describes the production of syndiotactic polypropylene with an object
to produce resin compositions having high stiffness when moulded. Metallcene
catalysts such as isopropyl(cyclopentadienyl-1-fiuorenyl) zirconium dichloride were
used in the production of the polypropylene. However the molecular weight, melting
point and syndiolacticity of these products were relatively low.
There is a need to develop new catalyst systems capable to provide polymers with
improved properties and efficient methods for preparing them.
It is an aim of the present invention to provide catalyst systems for the preparation of
polymers having high molecular weight
it is also an aim of the present invention to prepare polymers having a high melting
temperature.
it is another aim of the present invention to prepare impact copolymers having
improved impact properties.
It is a further aim of the present invention to prepare the catalyst systems capable to
provide these improved polymers.
Accordingly, the present invention provides a process for preparing a catalyst
component of general formula
Ra2C (3,6-Rb2-Flu) (2-Rc-4-Rd-C5H2) MQ2

wherein Ra2C is a mono-carbon bridge and wherein either both Ra arehydrogen or one Ra
is hydrogen and the other Ra is phenyl groups with or without substituents, such as herein
described, or both Ra are phenyl groups with substituents, such as herein described,
wherein Rb, Rc and Rd are each independently selected from H or alky having from 1 to
12 carbon atoms or aryl groups with or without substituents, such as herein described,
with the restriction that they are not all simultaneously hydrogen,
wherein M is a metal from Group 4 of the Periodic Table and
wherein Q is halogen or alkyl having from 1 to 12 carbon atoms, and
with the restriction that
when Rc is alkyl group and one Ra is unsubstituted phenyl group, the other Ra is
hydrogen,
when Rc is alkyl group and one Ra is substituted phenyl group, the other Ra may be
hydrogen or the same or another substituted phenyl group and the substituents are
electron withdrawing groups, such as herein described,
that when Rc is hydrogen, each Ra is independently selected form H or, with or without
substituents, such as herein described, phenyl group,
said process comprising:
a) reaction by nucleophilic addition, in a solvent, of the group (Ra2C-2-Rc-4- Rd -fulvene)
with the group [3,6-Rb2-Flu]- [M]+;
b) hydrolysis and separation of the resulting ligand;
c) deprotonation of the Iigand of step b) with R'M" to prepare a di-anion iigand, wherein
R' is an alkyl having from 1 to 6 carbon atoms and wherein M" is Li, Na or K;
d) salt metathesis reaction in a solvent of the di-anion Iigand of step c) with MQ4;
e) isolation of the catalyst component.
In a preferred embodiment according to the present invention in the bridge Ra2C,
one Ra is unsubstituted phenyl and the other Ra is H.
In another preferred embodiment, both Ra in the bridge are substituted phenyl
groups. The substituents on the phenyl groups preferably are electron withdrawing
groups that can be selected from halogen, more preferably F or CI, or from CX3
wherein X is a halogen, more preferably F, preferably F or from NO2. The
substituents on the phenyl groups can be located at position 4 in the case of a single

substituent, or at positions 3 and 5 for 2 if there are 2 substituents. Preferably both
phenyls have the same substitution pattern. Possible substituents to the "aryl groups"
are "halogen or CX3", wherein X is halogenf or C1-C6 alkyl.
Throughout this description, the positions are labelled as represented below.

Preferably, both Rb are the same and are alkyl having from 1 to 6 carbon atoms,
more preferably they both are tert-butyi.
Preferably Rc is H or methyl.
Preferably Rd is alkyl having from 1 to 6 carbon atoms, more preferably, it is tert-
butyl.
Preferably M is Zr, Hf or Ti, more preferably, it is Zr.
Preferably Q is halogen or methyl, more preferably it is chlorine.
Preferably, Ma is Li.
The solvent of steps a) and d) may be the same or different and are hydrocarbon,
preferably selected from pentane, toluene, tetrahydrofuran (THF) or diethyl ether
(Et2O). Preferably they are the same and it is H2O. Without Wishing to be bound by a
theory, it is believed Et2O stabilises a transition state of the nucleophilic addition

reaction including bulky constrained reagents. The reaction of step a) is carried out
at a temperature of from 0 to 60 °C, preferably at room temperature for a period of
time of from 6 to 24 hours, preferably of about 12 hours.
Any activating agent having an ionising action known in the art may be used for
activating the metallocene component- For example, it can be selected from
aluminium-containing or boron-containing compounds. The aluminium-containing
compounds comprise aluminoxane, alkyl aluminium and/or Lewis acid.
The aluminoxanes are preferred and may comprise oligomeric linear and/or cyclic
alkyl aluminoxanes represented by the formula:

wherein n is 1-40, preferably 10-20, m is 3-40, preferably 3-20 and R is a C1-C8 alkyl
group and preferably methyl.
Suitable boron-containing activating agents that can be used comprise a
triphenylcarbenium boronate such as tetrakis-pentafluorophenyl-borato-
triphenylcarbenium as described in EP-A-0427696, or those of the general formula

[L'-H] + [B Ar1 Ar2 X3 X4]- as described in EP-A-0277004 (page 6, line 30 to page 7,
line 7).
The catalyst system can also be supported. The support if present can be a porous
mineral oxide, advantageously selected from silica, alumina and mixtures thereof.
Preferably it is silica.
Alternatively, an activating support can be used.
The catalyst system of the present invention can be used in the polymerisation of
ethylene and alpha-olefins. It is preferably used to prepare highly isotactic propylene
homopolymers having a high weight average molecular weight of at least 500 kDa,
preferably at least 700 kDa, a high melting temperature of more than 150 °C,
preferably Of more than 160 °C, and an mmmm of more than 95.
It can also be used to prepare ethylene-propylene rubber (EPR) having an ethylene
content of from 8 to 15 wt%, a high weight average moiecuiar weight of at least 500
kDa, preferably at least 700 kDa, and a melt flow index MFI of from 2 to 10 dg/min.
The melt flow index is measured following the method of standard test ASTM D 1238
under a load of 2.16 kg and at a temperature of 230 oC. The EPR obtained in the
present invention is characterised by excellent impact properties. It can be used in
all applications that require elastomers with excellent thermoplastic properties.
List of Figures.
Figure 1 represents the reaction scheme for the preparation of complex H2C(3,6-
tBu2Fiu)(3-tBu-5-Me-Cp)ZrCi2(3).
Figure 2 represents the 1H NMR spectrum of ligand 3,6-di tert-buiyl-9-[(3-tert-butyl-5-
meihyicyciopenia-1 ,4-dien-1 -yl)methyl]-9H-fiuorene (2).

Figure 3 represents the 1H NMR spectrum of complex H2C(3,6-tBu2Flu)(3-tBu-5-Me-
Cp)ZrCI2(3).
Figure 4 represents the reaction scheme for the preparation of complex PhHC(3,6-
tBu2Flu)(3-tBu-5-Me-Cp)ZrCI2 (6).
Figure 5 represents the 1H NMR spectrum of 6-phenyl-2-methyl-4-tert-butyI-fulvene
(4).
Figure 6 represents the 1H NMR spectrum of ligand 3,6-Di-tert-butyl-9-[(4-tert-butyl-
2-methyl-cyclopenta-1,4-dienyl)-phenyl-ethyl]-9H-fluorene (5).
Figure 7 represents the 1HNMR spectrum of complex PhHC(3,6-tBu2Flu)(3-tBu-5-Me-
Cp)ZrCI2 (6).
Figure 8 represents the reaction scheme for the preparation of complex Ph2C(3,6-
tBu2-Flu)(3-tBu-Cp)ZrCI2 (9).
Figure 9 represents the reaction scheme for the preparation of complex (p-CI-
Ph)2C(3,6-tBu2Flu)(3-tBu-5-Me-Cp)ZrCI2(17).
Figure 10 represents the reaction scheme for the preparation of ligand 3,6-di-tert-
butyl-9-{(4-tert-butyI-2-methylcyclopenta-1,4-dien-1-yl)[bis(4-fluorophenyl)]methyl}-
9H-fluorene (19).
Figure 11 represents the reaction scheme for the preparation of ligand 9-[bis[3,5-
bis(trifluoromethyl)pheny|](4-tert-butyl-2-methylcyclopenta-1,4-dien-1-yl)methyl3-3,6-
di-tert-butyl-9H-fluorene (21).
Figure 12 represents the reaction scheme for the preparation of ligand 9-[[3,5-
bis(trifluoromethyl)phenyl](4-tert-butyl-2-methylcyclopenta-1,4-dien-1-yl)methyl]-3,6-
di-tert-butyl-9H-fluorene (23).

Examples.
All experiments were performed under purified argon atmosphere using standard
Schlenk techniques or in a glovebox. Solvents were distilled from Na/benzophenone
(tetrahydrofuran (THF), diethyl ether (Et2O)) and Na/K alloy (toluene, pentane) under
nitrogen, they were thoroughly degassed and stored under nitrogen. Deuterated
solvents (benzene-d6, toluene-d8, THF-d8; >99.5% D, Deutero GmbH) were vacuum-
transferred from Na/K alloy into storage tubes. Chloroform-d1 and CD2CI2 were kept
over calcium hydride and vacuum-transferred before use. The precursors 3,6,6'-
trimethyl-fulvene, 2-methyl-4-tert-butyl-cyclopentadiene (mixture of isomers) and 1-
methyl-3-tert-butyl-cyclopentadienyl lithium were prepared according to known
procedures and characterised by 1H NMR spectroscopy. 1-tert-butyl-cyclopentadiene
(mixture of isomers) was prepared according to a procedure described in Moore and
Jean King (Moore W.R. and Jean King B., J. Org. Chem., 36,1882,1971).
Synthesis of complex H2C(3,6-tBu2Flu)(3-tBu-5-Me-Cp)ZrCI2 (3).
The scheme is represented in figure 1.
a) Synthesis of 3,6-di-tert-butyl-9-[(3-tert-butyl-5-methylcyclopenta-1,4-dien-1-
vnmethyl]-9H-fluorene (2).
To a solution of 3.2 g (16.73 mmol) of 6-dimethylamino-2-methyl-4-tert-butyl-fulvene
in 50 ml. of THF were added, at room temperature, 50 mL of a solution of 3,6-di-tert-
butyl-fluorenyl-lithium prepared from 4.65 g (16.70 mmol) of 3,6-di-tert-butyl-fiuorene
and 6.70 mL (16.70 mmol) of a 2.5 M solution of n-butyl-lithium. The reaction mixture
was stirred for 12 h at room temperature. Then 1.17 g (30.79 mmol) of LiAIH4 were
added and the resulting mixture was refluxed for another 12 h and then carefully
quenched with 50 mL of a saturated solution of NH4CI diluted with 100 mL of diethyl
ether. The organic layer was separated, washed twice with 200 mL of water and
dried over CaCI2. All the volatiles were removed in vacuum. The crude yellow

product was purified by column chromatography over silica gel to give 4.27 g (10.02
mmol) of final product 2 with a yield of 60 % yield. This product was a 1:1 mixture of
double bond isomers in the cyclopentadienyl ring.
1H NMR (CDCI3, 300 MHz, 25 °C) spectrum is presented in Figure 2 and is
characterised as follows : 8 7.78 (s, 4H, Flu), 7.40-7.10 (m, 8H, Flu), 7.08 (dd, 1H,
Flu), 6.18 (s, 1H, Cp), 5.97 (d, 1H, Cp), 4.00 (q, 2H, 3J = 14.7 Hz, 9-Flu), 3.00 (m,
4H, CH2, Cp), 2.70 (m, 4H, CH2), 1.73, 1.66 (s, 3H, CH3), 1.42 (s, 36H, CCH3-Flu),
1.21 (s, 18H, CCH3-FIU).
Anal. Calcd for C32H42: C, 90.08; H, 9.92. Found: C, 91.01; H, 9.99.
b) Synthesis of the complex H9C(3,6-tBu2Flu)(3-tBu-5-Me-Cp)ZrCI2 (3).
To a solution of 1.67 g (3.91 mmol) 6-dimethylamino-2-methyl-4-tert-butyl-fulvene (1)
in 40 ml of Et2O were added 3.10 ml (7.82 mmol) of a 2.5 M solution of butyl-lithium
in hexane at 0 °C. The reaction mixture was stirred for 4 h and the solvent was
evaporated under reduced pressure. Then in glovebox 0.91 g (3.90 mmol) of
anhydrous ZrCI4 were added followed by the addition of 50 mL of pentane. The
resulting pink reaction mixture was stirred at room temperature overnight The
reaction mixture was filtered off and the filtrate was evaporated in vacuum. A portion
of about 30 mL of hexane was added and the resulting clear solution was kept at -30
°C overnight to give a pink microcrystalline powder precipitate of complex 3. A
second batch of 1.48 g (2.52 mmol) of product 3 was obtained from the mother
liqueur upon cooling with a yield of 64 %. Crystals suitable for X-ray diffraction were
obtained by slow concentration from a 3:7 CH2CI2/hexane mixture.
1H NMR (CD2CI2, 300 MHz, 25 °C) spectrum is presented in Figure 3 and is
characterised as follows : δ 8.01 (s, 1H, Flu), 7.97 (s, 1H, Flu), 7.52 (s, 1H, Flu), 7.40
(m, 2H, Flu), 7.37 (m, 1H, Flu), 6.02 (d, 1H, 4J = 2,8 Hz, Cp), 5.52 (d, 1H, 4J = 2,8
Hz, Cp), 4.74 (m, 2H, CH2), 2.16 (s, 3H, CH3), 1.44 (s, 9H, CCH3-FIU), 1.43 (s, 9H,
CCH3-Flu), 1.05 (s, 9H, CCH3-Flu).
13C NMR (CD2CI2, 75 MHz, 25 °C): 8 150.1,150.0,146.4,127.9, 127.6,124.8,
124.1,124.0,123.3,121.8,120.7,120.6,120.2,119.7,118.2,102.4, 97.0, 70.3,
35.6, 33.3, 32.2, 32.1, 32.0, 30.0, 22.5 (CH2), 16.1. Anal. Calcd for C32H40Cl2Zr : C,

65.50; H, 6.87; CI, 12.08. (Molecular mass Mr = 586.79 kg/mol) Found: C, 66.12; H,
6.99.
Synthesis of the complex Ph(H)C(3.6-tBu2Flu)(2-Me-4-tBu-Cp)ZrCI2 (6).
The scheme is represented in Figure 4.
a) Synthesis of 6-Dhenyl-2-methyl-4-tert-butyl-fulvene (4).
To a solution of 1.94 g (14.24 mmol) of 1-methyl-3-tert-butyl-cyclopentadiene
(mixture of isomers) in 50 mL of diethyl ether were added 5.7 mL (14.24 mmol) of a
2.5 M solution of butyllithium in hexane at 0 °C. The reaction mixture was stirred for
2 hours and a solution of 1.44 mL (14.24 mmol) of benzaldehide in 30 mL of ether
was added drop-wise. The reaction mixture became orange. After 2 hours, 50 mL of
a concentrated solution of NH4CI was added slowly. This mixture was stirred
overnight. The organic layer was separated, dried over MgSO4 and all the volatiles
were removed in vacuum. The orange residue was recrystallised from methanol at -
30 °C to give 1.0 g (4.46 mmol) of compound (1) with a yield of 31 %.
1H NMR (CDCl3, 300 MHz, 25 °C) spectrum is presented in Figure 5 and is
characterised as follows: δ 7.57 (m, 2H, Ph), 7.40 (m, 3H, Ph), 7.01 (s, 1H, =CHPh),
6.24 (t, 1H, CH), 6.14 (d, 1H, CH), 2.15 (s, 3H, CH3), 1.19 (s, 9H, CCH3).
13C NMR (CD2CI2, 75 MHz, 25 °C): 8160.4,145.9,137.4,135.5,131.9,129.5,
128.4,128.2,128.0,127.2,125.5,110.5, 32.1,29.5,12.6.
b) Synthesis of 3,6-Di-tert-butyl-9-[(4-tert-butyl-2-methyl-cyclopenta-1,4-dienyI)-
phenyl-ethyl]-9H-fluorene (5).
To a solution of 1,75 g (7.80 mmol) of compound (1) in 20 mL of THF were added,
at room temperature, 30 mL of a solution of 3,6-di-tert-bulyl-fluorenyl-lithium
prepared by reacting 1.95 g (7.00 mmol) of 3,6-di-tert-butyl-fluorene with 2.80 mL
(7.00 mmol) of a 2.5 M solution of n-butyl-lithium. The reaction mixture was stirred
for 4 h at ambient temperature (about 25 °C) and then quenched with 50 mL of a

saturated solution of NH4CI and diluted with 50 mL of diethyl ether. The organic layer
was separated, washed twice with 200 mL of water and dried over CaCI2. All the
volatiles were removed in vacuum and the residue was dissolved in hot MeOH. The
solution was cooled to -30 °C and a white precipitate formed. This latter was filtered
and washed with cold methanol (-30 °C) and dried in vacuum overnight to give 2.30
g (4.57 mmol) of final product (2) with a yield of 65 %. It contains about 20 % of
isomer 3,6-di-tert-butyl-9-[(4-tert-butyl-2-methylcyclopenta-1,3-dien-1-yl) (phenyl)
methyfJ-9H-fluorene.
1H NMR (CDCI3,300 MHz, 25 °C) spectrum is presented in Figure 6 and is
characterised as follows: δ 7.70 (dd, 2H, Flu), 7.35 (m, 5H, Ph), 7.08 (dd, 1H, Flu),
6.95 (dd, 1H, Flu), 6.83 (d, 1H, Flu), 6.29 (t, 2H, Flu), 4.48 (d, 1H, 3J= 10.6 Hz,
CHPh), 3.68 (d, 1H, 3J= 10.6 Hz, 9-Flu), 2.79 (s, 2H, CH2, Cp), 1.60 (s, 3H, CH3),
1.37 (s, 9H, CCH3-FIu), 1.33 (s, 9H, CCH3-Flu), 1.14 (s, 9H, CCH3-Flu).
13C NMR (CD2CI2, 75 MHz, 25 °C): 5 155.6,150.0,149.9,144.2,143.9,143.6,
141.4,141.3,139.9,139.8,134.6,128.9,128.7,128.6,126.4,125.6,125.3,124.7,
123.5,123.4,115.9,115.8, 51.0, 50.9,49.4, 44.0, 34.9, 33.2, 31.8, 31.1, 13.4.
c) Synthesis of the complex Ph(H)C(3,6-tBu2Flu)(2-Me-4-tBu-Cp)ZrCl2 (6).
To a solution of 1.025 g (2.04 mmol) of compound 2 in 40 ml of Et2O were added
1.67 mL (4.08 mmol) of a 2.5 M solution of butyl-lithium in hexane at 0 °C. The
reaction mixture was stirred for 4 h and then 0.475 g (2.04 mmol) of anhydrous ZrCU
were added in a glovebox. The resulting pink reaction mixture was stirred at room
temperature overnight. The solvent was then evaporated in vacuum and 40 mL of
hexane were condensed under reduced pressure. The resulting mixture was filtered
off and the filtrate was evaporated in vacuum to a give 1.18 g (1.78 mmol) of a pink
powder of crude complex (3) with a yield of 88 %. A new quantity of 20 mL of hexane
was added to the pink residue. After a period of time of from 1 to 2 hours, a pink
precipitate formed. It was isolated by decantation, washed with 10 mL of cold hexane
and dried in vacuum to yield 0.53 g (8.80 mmol) of di-chloro-zirconocene (3) with a
yield of 40 %. Crystals suitable for X-ray measurements were obtained by slow
concentration from a 1:9 CH2CI2/hexane mixture.

1H NMR (CD2CI2, 300 MHz, 25 °C) spectrum is presented in Figure 7 and is
characterised as follows: 8 8.03 (dd, 2H, Flu), 7.78 (d, 2H), 7.58 (d, 1H), 7.48 (m,
2H), 7.43 (m, 2H), 7.08 (dd, 1H, Flu), 6.57 (d, 1H, Flu), 6.50 (s, 1H, Cp), 6.12 (d, 1H,
4J = 2,6 Hz, Cp), 5.57 (d, 1H, 4J = 2,6 Hz, CHPh), 2.21 (s, 3H, CH3), 1.45 (s, 9H,
CCH3-FIU), 1.38 (s, 9H, CCH3-Flu), 1.05 (s, 9H, CCH3-Flu).
13C NMR (CD2CI2, 75 MHz, 25 °C) (Fig. 4): 5 150.2, 150.0,147.1,140.1,129.2,
128.9, 128.6, 128.4,128.2, 127.6,126.7, 125.9, 125.3,124.8,122.8,122.5,121.5,
120.0, 119.5, 119.3,116.9,103.2,100.9, 74.6, 40.2, 35.5, 35.4, 33.2, 32.0, 29.7,
15.8.
Anal. Calcd for C38H44Cl2Zr: C, 68.85; H, 6.69; CI, 10.70. (Mr = 662.885 kg/mol);
Found: C, 69.01; H, 7.37.
Synthesis of complex Ph2C(3,6-tBu2-Flu)(3-tBu-C5H3)ZrCl2 (9).
The scheme is represented in Figure 8.
a) Synthesis of Ph2C(3,6-tBu2-FluH)(3-tBu-C5H4) (8).
The reaction of sterically hindered stabilized 6,6'-diphenyl fulvenes with fluorenyl-
anion is known to proceed sluggishly and requires prolonged and significant heating.
The reaction between 6,6'-diphenyl-3-tert-butyl-fulvene (7) and fluorenyl-anion
appeared to depend upon the nature of the solvent Diethyl ether gave the best
results: the reaction proceeded over 5-7 days at a temperature of 60 to 70 °C to give
the desired product (8) with a yield of 21 %.
b) Synthesis of complex Ph2C(3,6-tBuyFlu)(3-tBu-C5H3)ZrCl2 (9).
Salt metathesis reaction between ligand (8) dianion generated in situ and ZrCl4 was
carried out. The reaction proceeded at room temperature in pentane with
concomitant precipitation of LiCI. After a usual workup the reaction mixture was kept
as a hexane solution for one month at room temperature to obtain red micro-crystals
of complex (9) with a yield of 46 %.

1H and 13C NMR spectroscopy of complex (9) displayed a dissymmetric structure in
solution similar to one described for complexes (3) and (6).
Synthesis of (p-CI-Ph)2C(3,6-di-tert-butyl-9fluorenyl)(2-Me-4-tert-butyl-
cvclopentadienyl) zirconium dichloride (17).
The scheme is represented in Figure 9.
a) Synthesis of 6,6'-bis(4-chloro-ohenyl)- 4-tert-butyl-2-methyl-fulvene (14).
To a solution of 2.27 g (16.66 mmol) of a mixture of isomers of 1-methyl-3-tert-butyl-
cyclopentadiene in 150 mL of tetrahydrofuran, were added 6.67 mL (16.66 mmol) of
a d 2.5 M solution of butyllithium in hexane, at 0 °C. The reaction mixture was stirred
for 2 hours and 4.18 g (16.66 mmol) of a solution of 4,4'-dichlorobenzophenone in 50
mL of THF were added dropwise. The reaction mixture turned orange. After 4 hours,
50 mL of a concentrated solution of NH4CI were added slowly. The mixture was
stirred overnight. The organic layer was separated, dried over MgSO4 and all the
volatiles were removed in vacuum. The orange residue was recrystallized from hot
methanol at 25 °C to give 3.7 g (10.02 mmol) of 6,6'-bis(4-chloro-phenyl)-2-methyl-4-
tert-butyl-fulvene with a yield of 60 % yield.
1H NMR (CDCI3l 400 MHz, 25 °C) is characterised as follows: δ 7.32 (m, 4H, Ph),
7.18 (m, 4H, Ph), 6.37 (s, 1H, Cp), 5.66 (s, 1H, Cp), 1.53 (s, 3H, CH3), 1.17 (s, 9H,
CCH3).
Anal. Calcd for C23H22CI2: C, 74.80; H, 7.00. Found: C, 74.85; H, 7.10.
b) Synthesis of 3.6-di-tert-butyl-9-((4-tert-butyl-2-methylcyclopenta-1,4-dien-1-
yl)[bis(4-chlorophenyl)]methyl}-9H-fluorene (15).
To a solution of 1.33 g (3.60 mmol) of 6,6'-bis(4-chloro-phenyl)-2-methyl-4-tert-butyl-
fulvene in 30 mL of Et2O were added, at room temperature, 30 mL of a solution of
3,6-di-tert-butyl-fluorenyl-lithium in Et2O, prepared from 1.0 g (3.59 mmol) of 3,6-di-
tert-butyl-fluorene and 1.44 mL (3.59 mmol) of a 2.5 M solution of n-butyl-lithium in

hexane. The reaction mixture was stirred for 5 days upon reflux and then quenched
with 50 mL of a saturated solution of NH4CI, diluted with 50 mL of diethyl ether. The
organic layer was separated, washed twice with 200 mL of water and dried over
CaCl2. All the volatiles were removed in vacuum. The residue was washed with
MeOH then with cold pentane at a temperature of -30 °C on a filter and dried in
vacuum overnight to give 1.4 g (2.16 mmol) of final product with a yield of 60 %.
Mass spectrum MS-ESI: m/z 645.7 , 370.3 ,277.4.
1H NMR (THF-d8, 300 MHz, 90 °C) is characterised as follows: 8 7.53 (br s, 2H, Flu),
7.40-6.80 (br m, 14H, Ph and Flu), 6.20 (br s, 1H, Cp), 5.64 (s, 1H, 9-Flu), 2.78 (s,
2H, CH2, Cp), 1.36 (s, 3H, CH3), 1.32 (s, 18H, CCH3-Flu), 1.09 (s, 9H, CCH3-Flu).
13C NMR (THF-d8, 75 MHz, 90 °C): 5 151.0, 150.1, 149.8, 144.7, 144.3, 143.5,
143.3, 143.2, 141.8, 135.0, 133.7, 133.1, 131.9, 131.5, 130.1, 129.6, 128.9, 127.1,
126.5, 125.3, 123.9, 116.5, 116.3, 116.2, 57.1, 55.4, 41.3, 35.2, 32.5, 31.9, 31.8,
28.9, 28.7, 28.3.
Anal. Calcd for C44H48CI2: C, 81.58; H, 7.47. Found: C, 82.04; H, 8.55.
The zirconocene (17) was then obtained by reaction with anhydrous ZrCl4 following
the same scheme as that depicted for preparing complex (3) or complex (6).
Alternatively, each phenyl group in the bi-phenyl bridge can be substituted by
fluorine at position as shown on figure 10 or by two CF3 respectively at positions 3
and 5 as shown on figure 11.
Synthesis of (3,5-bis(trifluoromethyl)-phenyl)CH(3,6-di-tert-butyl-9fluorenyl)(2-
Me-4-tert-butyl-cyclopentadienyl) zirconium dichloride (24).
a) Synthesis of 6-(3,5-bis(trifluoromethyl)-henyl)-3-tert-butyl-5-methyl-fulvene (22).
To a solution of 2.81 g, (20.63 mmol) of a mixture of isomers of 1-metbyl-3-tert-butyl-
cyclopentadienyl in 150 mL of diethyl ether, were added 8.20 mL (20.63 mmol) of a
2.5 M solution of butyilithium in hexane, at 0 °C. The reaction mixture was stirred for
2 hours and a solution of 5.0 g (20.65 mmol) of 3,5-bis(trifluoromethyl)benzaldehide

in 50 mL of ether was added dropwise. The reaction mixture turned red. After 2
hours, 50 mL of a concentrated solution of NH4CI was added slowly. This mixture
was stirred overnight. The organic layer was separated, dried over MgSO4 and all
the volatiles were removed in vacuum. The orange residue was recrystallized from
methanol at -30 °C to give 2.60 g (7.22 mmol) of compound 22 with a yield of 35 %.
1H NMR (CDCI3, 300 MHz, 25 °C) is characterised as follows: δ 7.92 (s, 2H, Ph),
7.79 (s, 1H, Ph), 6.95 (s, 1H, =CHPh), 6.25 (t, 1H, CH), 5.92 (d, 1H, CH), 2.11 (s,
3H, CH3), 1.15 (s, 9H, CCH3). 19F NMR (CDCI3, 282 MHz, 25 °C): δ -62.6.
Anal. Calcd for C34H32F2: C, 62.98; H, 5.56. Found: C, 63.67; H, 5.98.
b) Synthesis of 9-[[3,5-bis(trifluoromethyl)phenyl](4-tert-butyl-2-methylcyclopenta-
1,4-dien-1-yl)methyl]-3,6-di-tert-butyl-9H-fluorene (23).
The scheme for preparing component (23) is represented in Figure 12.
To a solution of 2.60 g (7.21 mmol) of compound 22 in 25 mL of THF, were added,
at room temperature, 30 mL of a solution of 3,6-di-tert-butyl-fluorenyl-lithium
prepared from 2.00 g (7.20 mmol) of 3,6-di-tert-butyl-fluorene and 2.90 mL (7.21
mmol). of a 2.5 M solution of n-butyl-lithium. The reaction mixture was stirred for 4 h
at room temperature and then quenched with 50 mL of a saturated solution of NH4CI
diluted with 50 mL of diethyl ether. The organic layer was separated, washed twice
with 200 mL of water and dried over CaCl2. All the volatiles were removed in
vacuum. The residue was purified by column chromatography over silica gel using
hexane as an eluent to give 0.2 g (0.31 mmol) of final compound 23 as a mixture of
two isomers in relative amounts of 2:3 with a yield of 4 %.
1H NMR (CDCI3, 300 MHz, 25 °C) is characterised as follows: δ 7.70 (m, 3H, Ph),
7.20-6.30 (m, 6H, Flu), 6.20 (s, 1H, Cp), 5.91 (s, 1H, Cp), 4.48 (m, 1H, CHPh), 3.95
(m, 1H, 9-Flu), 3.19-2.73 (m, 2H, CH2, Cp), 1.59-1.52 (s, 3H, CH3), 1.36-1.33 (s,
18H, CCH3-Flu), 1.16-1.14 (s, 9H, CCH3-Flu).
19F NMR (CDCI3, 282 MHz, 25 °C): 8 -62.41, -62.45.
Anal. Calcd for C40H44F6: C, 75.21; H, 6.94. Found: C, 76.14; H, 7.01.

The zirconocene (24) was then prepared following the method used to prepare
components (3) and (6).
The catalyst components synthetised here-above were tested in the homo- or co-
polymerisation of propylene. They were activated with methylaluminoxan (MAO) and
optionally deposited on a silica support: they produced highly isotactic
homopolymers of propylene or ethylene-propylene rubber (EPR) having excellent
impact properties. The polymerisation conditions and results are displayed in Table I
for heterogeneous polymerisation and in Table II for homogeneous polymerisation.

All resins produced with the new catalyst system according to the present invention
had very high molecular weights and melting temperature.
Additional examples carried out on the copolymerisation of ethylene with propylene
led to ethylene-propylene rubber having high viscosity, high molecular weight and
melt flow rate smaller than 10 dg/min and thus excellent impact properties. With prior
art catalyst systems, the molecular weight of the EPR was very low with a very low
viscosity leading to bad impact properties.

WE CLAIM:
1. A process for preparing a catalyst component of general formula
Ra2C (3,6-Rb2-Flu) (2-Rc-4-Rd-C5H2)MQ2
wherein Ra2C is a mono-carbon bridge and wherein either both Ra are hydrogen or one Ra
is hydrogen and the other Ra is phenyl groups with or without substituents, such as herein
described, or both Ra are phenyl groups with substituents, such as herein described,
wherein Rb, Rc and Rd are each independently selected from H or alkyl having from 1 to
12 carbon atoms or aryl groups with or without substituents, such as herein described,
with the restriction that they are not all simultaneously hydrogen,
wherein M is a metal from Group 4 of the Periodic Table and
wherein Q is halogen or alkyl having from 1 to 12 carbon atoms, and
with the restriction that
when Rc is alkyl group and one Ra is unsubstituted phenyl group, the other Ra is
hydrogen,
when Rc is alkyl group and one Ra is substituted phenyl group, the other Ra may be
hydrogen or the same or another substituted phenyl group and the substituents are
electron withdrawing groups, such as herein described,
that when Rc is hydrogen, each Ra is independently selected form H or, with or without
substituents, such as herein described, phenyl group,
said process comprising:
a) reaction by nucleophiiic addition, in a solvent, of the group (Ra2C-2-Rc-4- Rd -fulvene)
with the group [3,6-Rb2-Flu]- [M']+;
b) hydrolysis and separation of the resulting ligand;
c) deprotonation of the ligand of step b) with R'M" to prepare a di-anion ligand, wherein
R' is an alkyl having from 1 to 6 carbon atoms and wherein M" is Li, Na or K;
d) salt metathesis reaction in a solvent of the di-anion ligand of step c) with MQ4;
e) isolation of the catalyst component.

2. The process as claimed in claim 1, wherein the substituents on the phenyl groups, if
present, are at position 4 for a single substituent or at positions 3 and 5 for 2 substituents.
3. The process as claimed in claim 1 or claim 2, wherein both Rb are the same and are tert-
butyl.

4. The process as claimed in any one of preceding claims, wherein Rc is methyl at position 2
and Rd is tert-butyl at position 4.
5. The process as claimed in any one of the preceding claims, wherein the solvent of step a)
is Et2O.
6. The process as claimed in claim 5, wherein the solvent in step d) is also Et2O.
7. The process as claimed in any one of the preceding claims wherein M" is Li.

8. Process for preparing ethylene-propylene rubber, employing the metallocene catalyst
component obtained by the process as claimed in any of claims 1 to 7, in combination
with an activating agent, such as herein described, the ethylene-propylene rubber, so
prepared, having an ethylene content of from 8 to 15 wt%, a weight average molecular
weight of at least 500 kDa and excellent impact properties.
9. The process for preparing isotactic polypropylene, employing the metallocene catalyst
component obtained by the process as claimed in any of claims 1 to 7, in combination
with an activating agent, such as herein described, said isotactic polypropylene, so
prepared, having a weight average molecular weight of more than 500 kDa, a melting
temperature of more than 150 °C and an mmmm of more than 95.

ABSTRACT

CARBON-BRIDGED CYCLOPENTADIENYL-FLUORENYL LIGANDS
There is a process for preparing a catalyst component of general formula
Ra2C (3,6-Rb2-Flu) (2-Rc-4-Rd-C5H2)MQ2
wherein Ra2C is a mono-carbon bridge and wherein either both Ra are hydrogen or one Ra
is hydrogen and the other Ra is phenyl groups with or without substituents, such as herein
described, or both Ra are phenyl groups with substituents, such as herein described,
wherein Rb, Rc and Rd are each independently selected from H or alkyl having from 1 to
12 carbon atoms or aryl groups with or without substituents, such as herein described,
with the restriction that they are not all simultaneously hydrogen,
wherein M is a metal from Group 4 of the Periodic Table and
wherein Q is halogen or alkyl having from 1 to 12 carbon atoms, and
with the restriction that
when Rc is alkyl group and one Ra is unsubstituted phenyl group, the other Ra is
hydrogen,
when Rc is alkyl group and one Ra is substituted phenyl group, the other Ra may be
hydrogen or the same or another substituted phenyl group and the substituents are
electron withdrawing groups, such as herein described,
that when Rc is hydrogen, each Ra is independently selected form H or, with or without
substituents, such as herein described, phenyl group,
said process comprising:
b) reaction by nucleophilic addition, in a solvent, of the group (Ra2C-2-Rc-4- Rd -fulvene)
with the group [3,6-Rb2-Flu]- [M']+;
b) hydrolysis and separation of the resulting ligand;
c) deprotonation of the ligand of step b) with R'M" to prepare a di-anion ligand, wherein
R' is an alkyl having from 1 to 6 carbon atoms and wherein M" is Li, Na or K;
d) salt metathesis reaction in a solvent of the di-anion ligand of step c) with MQ4;
e) isolation of the catalyst component.

CARBON-BRIDGED CYCLOPENTADIENYL-FLUORENYL LIGANDS

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