METAL COMPLEX COMPRISING AMIDINE AND SUBSTITUTED CYCLOPENTADIENYL LIGANDS

Abstract

A metal complex of the formula (1) CyLMZ.sub.p(A).sub.n (1), wherein M is a group 4 metal Z is an anionic ligand, p is number of 1 to 2, preferably 2, Cy is a cyclopentadienyl-type ligand substituted with at least one aliphatic C.sub.3-C.sub.20 hydrocarbyl group, which is bonded to the cyclopentadienyl-type ligand, in particular to its cyclopentadienyl ring, via a secondary, a tertiary or quaternary carbon atom and, L is an amidinate ligand of the formula (2), wherein the amidine-containing ligand is covalently bonded to the metal M via the imine nitrogen atom, and Sub1 is a substituent comprising a group 14 atom through which Sub1 is bonded to the imine carbon atom and Sub2 is a substituent comprising a heteroatom of group 15, through which Sub2 is bonded to the imine carbon atom and A is a neutral Lewis base ligand selected from the list consisting of ether, thioether, amine, tertiary phosphane, imine, nitrile and isonitrile, wherein the number of said metal ligands “n” is in the range of 0 to the amount that specifies the 18-electron rule.

##STR00001##

Claims

1. A metal complex of the formula (1)
CyLMZ.sub.p(A).sub.n  (1), wherein: M is a group 4 metal, Z is an anionic ligand, p is number of 1 to 2, Cy is a cyclopentadienyl-type ligand substituted with at least one aliphatic C.sub.3-C.sub.20 hydrocarbyl group, which is bonded to the cyclopentadienyl-type ligand via its cyclopentadienyl ring, via a secondary, a tertiary or quaternary carbon atom, and L is an amidinate ligand of the formula (2) ##STR00007## wherein the amidinate ligand is covalently bonded to the metal M via the imine nitrogen atom, and Sub1 is a substituent comprising a group 14 atom through which Sub1 is bonded to the imine carbon atom and Sub2 is a substituent comprising a heteroatom of group 1$, through which Sub2 is bonded to the imine carbon atom, and A is a neutral Lewis base ligand selected from the group consisting of ether, thioether, amine, tertiary phosphene, imine, nitrile and isonitrile, wherein the number “n” of the metal ligands is 0 to the amount that specifies the 18-electron rule.

2. The metal complex according to claim 1, wherein M is titanium.

3. The metal complex according to claim 1, wherein Z independently means a halogen atom, a C.sub.1-10 alkyl group, a C.sub.7-20 aralkyl group, a C.sub.6-20 aryl group, or a C.sub.1-20 hydrocarbon-substituted amino group.

4. The metal complex according to claim 1, wherein: Sub1 comprises a phenyl or substituted phenyl residue, and Sub2 comprises an amino radical of the formula —NR.sup.4R.sup.5, with R.sup.4 and R.sup.5 being individually selected from the group consisting of aliphatic hydrocarbyl, halogenated aliphatic hydrocarbyl, aromatic hydrocarbyl, and halogenated aromatic hydrocarbonyl residues, whereby R.sup.4 optionally forms a heterocyclic structure with R.sup.5 or Sub1.

5. The metal complex according to claim 1, wherein: M is Ti, Z is selected from the group consisting of chlorine and C.sub.1-C.sub.4-alkyl, p is 2, Cy is a tert-butylcyclopentadienyl, L means N,N-diisopropylbenzamidinate, 2,6-difluoro-N,N-diisopropylbenzamidinate or pentafluoro-N,N-diisopropylbenzamidinate, and A means THF with n meaning 0 or 1.

6. The metal complex of formula (1) according to claim 1, wherein the formula (1) having a ligand L of the formula 2b) ##STR00008## wherein: the amidinate ligand is covalently bonded to the metal M via the imine nitrogen atom N.sup.2; S is a —CH.sub.2— unit, and t is an integer number denoting the number of S, and is 1-4, more preferably 1-2, and most preferably 1; Sub3 is an aliphatic or aromatic cyclic or linear substituent comprising a group 14 atom through which Sub3 is bonded to the amine nitrogen atom N.sup.1; and Sub4 is an optionally substituted bidentate C2 unit in which the 2 carbon atoms may be sp.sup.2 or sp.sup.3 hybridized.

7. A process for manufacturing the metal complex of formula (1) according to claim 1, the process comprising: reacting a metal complex of the formula (3)
CyMZ.sub.p+1  (3) with a neutral Lewis base A to form the metal complex of the formula CyMZ.sub.p+1 (A).sub.n, wherein the radicals Cy, A, M, p and n have the meanings according to claim 1, and Z means halogen, in particular Cl, Br, or F, and subsequently reacting the metal complex of the formula CyMZ.sub.p+1(A).sub.n with an amidine of the formula LH or its hydrohalogen acid salt LH.HZ, wherein L has the meaning according to claim 1, and Z means halogen, in particular Cl, Br, or F, to produce the metal complex of formula (1).

8. A catalyst system comprising: a) the metal complex of the formula (1) according to claim 1, b) an activator, and c) optionally a scavenger.

9. The catalyst system according to claim 8, wherein the system comprises the scavenger, and the scavenger c) is a hydrocarbyl of a metal or metalloid of group 1-13, or its reaction products with at least one sterically hindered compound containing a group 15 or 16 atom.

10. The catalyst system according to claim 8, wherein the activator b) is a borane, a borate, or an organoaluminum compound (E), preferably alkylaluminoxane.

11. A process for preparing a polymer by polymerizing at least one olefinic monomer, the process comprising contacting the olefinic monomer with the metal complex according to claim 1 or a catalyst system comprising the metal complex according to claim 1.

12. The process according to claim 11, wherein the olefinic monomers comprise ethylene and at least a C.sub.3-C.sub.12-α-olefin.

13. The process according to claim 11, wherein the olefinic monomers comprise ethylene, at least one C.sub.3-12 alpha olefin, and at least one non-conjugated diene, preferably selected from the group consisting of 5-methylene-2-norbornene 5-ethylidene-2-norbornene, 5-vinylnorbornene, 2,5-norbornadiene, dicyclopentadiene, and vinylcyclohexene, in particular from the group consisting of 5-ethylidene-2-norbornene, and 5-vinylnorbornene.

14. Polymers obtained with the metal complex according to claim 1, or with a catalyst system comprising the metal complex according to claim 1.

15. The metal complex according to claim 2, wherein: Z independently means a halogen atom, a C.sub.1-10 alkyl group, a C.sub.7-20 aralkyl group, a C.sub.6-20 aryl group or a C.sub.1-20 hydrocarbon-substituted amino group; Sub1 is a phenyl or substituted phenyl residue; and Sub2 is an amino radical of the formula —NR.sup.4R.sup.5, with R.sup.4 and R.sup.5 being individually selected from the group of aliphatic hydrocarbyl, halogenated aliphatic hydrocarbyl, aromatic hydrocarbyl, halogenated aromatic hydrocarbonyl residues, whereby R.sup.4 optionally forms a heterocyclic structure with R.sup.5 or Sub1.

16. The metal complex according to claim 2, wherein: Z is selected from the group consisting of chlorine and C.sub.1-C.sub.4-alkyl, p is 2, Cy is a tert-butylcyclopentadienyl, A is THF with n being 0 or 1, and L is of the formula 2b) ##STR00009## wherein: the amidinate ligand is covalently bonded to the metal M via the imine nitrogen atom N.sup.2; S is a —CH.sub.2— unit, and t is 1; Sub3 is an aliphatic or aromatic cyclic or linear substituent comprising a group 14 atom through which Sub3 is bonded to the amine nitrogen atom N.sup.1; and Sub4 is an optionally substituted bidentate C2 unit in which the 2 carbon atoms may be sp.sup.2 or sp.sup.3 hybridized.

Description

EXAMPLES

[0091] Test methods. [0092] Size Exclusion Chromatography with IR detector (SEC-IR) [0093] Equipment: Freeslate Rapid GPC system with single detection (Infrared detector IR4 Standalone by Polymer Char) [0094] Columns: PLGel Mixed-B 10 μm (×3 300×7.5 mm columns) [0095] Calibration: Calibration with linear polystyrene (PS) standards (molecular weight ca. 30-3000 kg/mol) [0096] Temperature: 160° C. [0097] Flow: 1.5 ml/min [0098] Injection volume: 125 μl [0099] Solvent/eluent: Distilled 1,2,4-trichlorobenzene with 0.4 g/l of BHT stabilizer [0100] Sample preparation: Dissolving for 2 hours at approx. 160° C. [0101] Filtration through 2 and 0.5 micron sintered glass filter [0102] Sample concentration 1.5 mg/ml

[0103] NMR (.sup.1H, 300 MHz, .sup.13C 75.4 MHz, .sup.19F 282 MHz) spectra were measured on a Bruker Avance 300 spectrometer.

[0104] Fourier transformation infrared spectroscopy (FT-IR), was used to determine the composition of the copolymers according to the method that is known in the art. The FT-IR measurement gives the composition of the various monomers in weight percent relative to the total composition.

[0105] Composition was determined using mid-range FT-IR spectroscopy (in the cases of Tables 1 and 2 using polymer samples deposited on gold-coated silicon wafers).

[0106] Intrinsic Viscosity (IV) (Tables 3-6) was measured at 135° C. in decahydronaphthalene as solvent (Ubbelohde). IV (Tables 1-2) is calculated from the Mw value (SEC-IR) with reference to a calibration line correlating Mw (SEC-IR 160° C.) and IV (Ubbelohde 135° C.).

Part I: Synthesis of Ligands and Compounds

General.

[0107] All manipulations were carried out using standard Schlenk line or dry-box techniques under an atmosphere of argon or dinitrogen. Solvents were degassed by sparging with dinitrogen and dried by passing through a column of the appropriate drying agent. Toluene was refluxed over sodium and distilled. Deuterated solvents were dried over potassium (C.sub.6D.sub.6) or P.sub.2O.sub.5 (CDCl.sub.3 and CD.sub.2Cl.sub.2), distilled under reduced pressure and stored under dinitrogen in Teflon valve ampoules. NMR samples were prepared under dinitrogen in 5 mm Wilmad 507-PP tubes fitted with J. Young Teflon valves. .sup.1H and .sup.13C-{.sup.1H} spectra were recorded at ambient temperature and referenced internally to residual protio-solvent (.sup.1H) or solvent (.sup.13C) resonances, and are reported relative to tetramethylsilane (d=0 ppm). Chemical shifts are quoted in δ (ppm) and coupling constants in Hz.

Synthesis of Ligands and Literature Compounds

[0108] Ligand A (2-(phenyl)-2,3-dihydro-isoindol-1-ylideneamine)

[0109] A Schlenk tube was charged with aniline (5.000 g, 53.69 mmol) dissolved in p-cymene (50 mL) and 2-(bromomethyl)benzonitrile (10.526 g, 53.69 mmol) under inert conditions. This was left stirring at 150° C. for 16 hours. The p-cymene was removed from the resulting white powder by filtration. The powder was washed with 3×50 mL toluene, and then with n-hexanes (3×50 mL), using a filter cannula, and remaining n-hexane was removed in vacuo, yielding 14.33 g of the hydrobromide salt of the ligand (92.3%). .sup.1H NMR (300 MHz, DMSO-d.sup.6, R.T.); δ 10.20 (s, 1H, NH), 9.20 (s, 1H, NH), 8.46-7.58 (m, 9H, Ar—H), 5.35 (s, 2H, CH.sub.2).

[0110] The neutral protio ligand A was obtained by neutralization of a diethylether solution the hydrobromide salt using 4 M NaOH (aq)), removal of the aqueous phase and evaporation of the volatiles under reduced pressure.

[0111] Ligand B (HNC(C.sub.6F.sub.5)(.sup.iPr.sub.2N))

[0112] AlCl.sub.3 (1.07 g, 8.00 mmol) was placed in a microwave vial, and pentafluorobenzonitrile (1.00 mL, 8.00 mmol) was added. The vial was capped and put in an oil bath that was preheated to 110° C. When a uniform melt formed, diisopropylamine (1.35 mL, 9.60 mmol) was added. The reaction mixture was stirred for 3 hours, allowed to cool down to rt and quenched by addition of icewater (4 mL). The reaction mixture was partitioned between HCl solution (1 M, aqueous 20 mL) and EtOAc (20 mL). The organic phase was extracted with HCl solution (1 M, aqueous 20 mL), and the combined aqueous fractions were basified (NaOH, 4 M, aqueous) and extracted with EtOAc (3×20 mL). The combined organic fractions were then dried (Mg.sub.2SO.sub.4), filtered and concentrated in vacuo to yield the product (1.425 g, 60%) as brownish crystals. Subsequent sublimation at 65° C./0.6 mbar yielded colourless crystals (1.35 g, 90%). The overall yield was 54%.

[0113] .sup.1H-NMR (300 MHz, CDCl.sub.3) δ: 6.33 (1H, br. s., NH); 4.0-3.2 (2H, m., (CH.sub.3).sub.2CH); 1.9-0.9 (12H, m., (CH.sub.3).sub.2CH,). .sup.19F-NMR (282 MHz, CDCl.sub.3) δ: −142.63 (2F, m., ortho-C.sub.6F.sub.5); −154.65 (1F, m., para-C.sub.6F.sub.5); −160.75 (2F, m., meta-C.sub.6F.sub.5).

[0114] Ligand C (HNC(2,6-C.sub.6H.sub.3F.sub.2)(NC.sub.5H.sub.10))

[0115] To a piperidine (5 mL, 50.6 mmol) solution in toluene (20 mL) was added MeMgCl (3.0 M in THF, 16.9 mL, 50.6 mmol). The solution was heated to 50° C., for two hours before allowing to cool to room temperature and transferring using a cannula to a solution of 2,6-difluorobenzonitrile (7.03 g, 50.6 mmol) in toluene (20 mL). The solution was stirred for 16 h at room temperature after which time the reaction was quenched by addition of water (1 mL). After stirring for an hour, anhydrous sodium sulfate was added and the solution was then filtered to remove salts. The clear solution was then washed with brine (2×40 mL) before removal of the volatiles under reduced pressure to yield a viscous yellow oil. This was then diluted with another portion of hexanes (15 mL) and placed at −20° C. for two days resulting in crystallization of the desired product. Yield=8.7 g (77%). .sup.1H NMR (300 MHz) (CDCl.sub.3) δ (ppm): 7.24 (m, 1H, Ar); 6.86 (m, 2H, Ar); 6.06 (m, 1H, NH), 3.33 (br m, 4H, NCH.sub.2), 1.53 (br m, 6H, CH.sub.2CH.sub.2CH.sub.2) ppm. .sup.19F-NMR (282 MHz, CDCl.sub.3) δ: −113.30 ppm.

[0116] Ligand D (2-(cyclooctyl)-2,3-dihydro-isoindol-1-ylideneamine)

[0117] 2-(Bromomethyl)benzonitrile (3.00 g, 15.3 mmol) and cyclooctylamine (1.95 g, 15.3 mmol) were mixed without solvent at room temperature. The reaction was performed at room temperature for 5 min. The resulting dark gel was washed with diethylether (3×20 mL) to yield the product as a white solid (3.72 g, 11.5 mmol, 75%). The hydrobromide salt of the ligand was isolated as a powder which was characterized by .sup.1H NMR (300 MHz) (CDCl.sub.3) δ (ppm): 1.7 (m, 15H); 4.7 (s, 2H); 5 (s, 1H); 7.6 (m, 4H) and .sup.13C NMR (75 MHz) (CDCl.sub.3) δ (ppm): 24.2; 27.4; 31.3; 52.3; 56.9; 126.7; 129.4; 160.8.

[0118] The neutral protio ligand D was obtained by neutralization of a diethylether solution the hydrobromide salt using 4 M NaOH (aq).

[0119] Ligand E (HNC(Ph)(.sup.iPr.sub.2N)) was prepared as described in WO 2005/090418.

[0120] Ligand F (HNC(3,5-C.sub.6H.sub.3F.sub.2)(.sup.iPr.sub.2N))

[0121] Synthesized according to the procedure described for Ligand B in a yield of 704 mg (58%). .sup.1H-NMR (300 MHz, CDCl.sub.3) δ: 6.84-6.73 (3H, m, ArH); 5.95 (1H, r. s., NH); 3.57 (2H, septet., J=6.8, (CH.sub.3).sub.2CH); 1.32 (12H, d, J=6.8, (CH.sub.2).sub.2CH). .sup.13C-NMR (75 MHz, CDCl.sub.3) δ: 165.52 (iPr.sub.2NC═NH); 163.36 (d., J=250.4, meta-C.sub.6H.sub.3F.sub.2); 163.20 (d., J=250.4, meta-C.sub.6H.sub.3F.sub.2); 144.34 (t., J=8.5, ipso-C.sub.6H.sub.3F.sub.2); 109.55 (dd, J=8.3, 17.3, ortho-C.sub.6H.sub.3F.sub.2); 103.99 (t., J=25.2, para-C.sub.6H.sub.3F.sub.2); 48,85 (CH.sub.3).sub.2CH), 21.10 (CH.sub.3).sub.2CH). .sup.19F-NMR (282 MHz, CDCl.sub.3) δ: −108.99 (2F, s., meta-C.sub.6H.sub.3F.sub.2).

[0122] Ligand G (2-(cyclohexyl)-2,3-dihydro-isoindol-1-ylideneamine)

[0123] 2-(Bromomethyl)benzonitrile (4.90 g, 25.0 mmol) was dissolved in toluene (10 mL) and cyclohexylamine (2.48 g, 25.0 mmol), dissolved in toluene (10 mL), was added dropwise within 20 min. It was stirred at 50° C. overnight. The solvent was evaporated to approx. 10 mL and diethylether (20 mL) was added. It was filtered off, washed with diethylether (2×20 mL) and dried under reduced pressure to yield the product as a white solid (6.71 g, 22.8 mmol, 91%).

[0124] The hydrobromide salt of the ligand was isolated as a powder which was characterized by .sup.1H NMR (300 MHz) (CDCl.sub.3) δ (ppm): 1.10-2.14 (10H, m); 4.67 (2H, s); 4.95 (1H, m); 7.51 (1H, d); 7.58-7.68 (2H, m); 9.05 (1H, d); 9.81 (1H, s); 10.25 (1H, s).

[0125] The neutral protio ligand G was obtained by neutralization of a dichloromethane solution the hydrobromide salt using 4 M NaOH (aq), removal of the aqueous phase and evaporation of the volatiles under reduced pressure.

[0126] Ligand H (HNC(2,4,6-C.sub.6H.sub.2F.sub.3)(.sup.iPr.sub.2N))

[0127] Synthesized according to the procedure described for Ligand B in a yield of 795 mg (44%). .sup.1H-NMR (300 MHz, CDCl.sub.3) δ: 6.75-6.65 (2H, m, ArH); 6.15 (1H, br. s., NH); 3.94-3.22 (2H, m., (CH.sub.3).sub.2CH); 1.95-0.75 (12H, m., (CH.sub.3).sub.2CH,). .sup.19F-NMR (282 MHz, CDCl.sub.3) δ: −108.08 (1F, t., J=5.9, para-C.sub.6F.sub.5); −111.44 (2F, d., J=5.9, ortho-C.sub.6F.sub.5).

[0128] Ligand I (HNC(2,6-C.sub.6H.sub.3F.sub.2)(.sup.iPr.sub.2N)) was prepared as described in WO 2005/090418.

[0129] Ligand J (HNC(2,4-C.sub.6H.sub.4F.sub.2)(.sup.iPr.sub.2N))

[0130] Synthesized according to the procedure described for Ligand B in a yield of 780 mg (46%). .sup.1H-NMR (300 MHz, CDCl.sub.3) δ: 7.22 (1H, td., J=8.2, 6.4 ortho-ArH); 6.93-6.77 (2H, m., meta-ArH); 6.00 (1H, br. s., NH); 3.58 (2H, septet., J=6.8, (CH.sub.3).sub.2CH); 1.32 (12H, d, J=6.8, (CH.sub.2).sub.2CH). .sup.13C-NMR (75 MHz, CDCl.sub.3) δ: 162.97 (dd., J=250.1, 11.5, ortho-CF); 161.17 (iPr.sub.2NC═NH); 158.44 (dd., J=250.2, 11.9, para-CF); 129.59 (dd., J=9.6, 5.5, ortho-CH); 125.33 (dd., J=18.4, 4.1, ipso-CH); 112.03 (dd, J=21.4, 3.7, CFCHCH); 104.58 (t, J=25.5, CFCHCF); 48.93 (CH.sub.3).sub.2CH), 20.99 (CH.sub.3).sub.2CH). .sup.19F-NMR (282 MHz, CDCl.sub.3) δ: −109.98 (d, J=7.7), −112.30 (d, J=7.6).

[0131] Ligand K (2-(2,6-difluorophenyl)-2,3-dihydro-isoindol-1-ylideneamine)

[0132] A Schlenk tube was charged with 2,6-difluoroaniline (1.000 g, 5.10 mmol) dissolved in p-cymene (5 mL) and 2-(bromomethyl)benzonitrile (0.549 g, 5.10 mmol) under inert conditions and heated at 150° C. for 16 hours. The resulting powder was washed with toluene (3×5 mL), and then with n-hexane (3×5 mL), and dried in vacuo yielding 1.58 g of the hydrobromide salt of the ligand (95.3%).

[0133] .sup.1H NMR (300 MHz, DMSO-d.sup.6, R.T.); δ 10.78 (s, 1H, NH), 9.96 (s, 1H, NH), 8.51-7.50 (7H, Ar—H), 7.80, 5.33 (s, 2H, CH.sub.2). .sup.19F NMR (282 MHz, DMSO-d.sup.6, R.T.); δ −118.05.

[0134] The neutral protio ligand K was obtained by neutralization of a dichloromethane solution the hydrobromide salt using 4 M NaOH (aq)), removal of the aqueous phase and evaporation of the volatiles under reduced pressure.

[0135] Compound P Cp*TiCl.sub.3 was bought from Boulder Scientific Company and used as received.

[0136] Compound Q .sup.tBuCpTiCl.sub.3 was prepared as described in Macromolecules 2000, 33, 2796-2800.

[0137] Compound T (CpTiCl.sub.2(NC(Ph)(.sup.iPr.sub.2N)) was prepared as described for compound 5 in WO 2005/090418.

[0138] Compound U Me.sub.5CpTiCl.sub.2(NC(Ph)(.sup.iPr.sub.2N)) was prepared as described for compound 6 in WO 2005/090418

[0139] Compound UM Me.sub.5CpTiMe.sub.2(NC(Ph)(.sup.i Pr.sub.2N))

[0140] To a stirring toluene (15 mL) solution of Cp*Ti{NC(Ph)N.sup.iPr.sub.2}Cl.sub.2 (Compound B) (1.00 g, 2.20 mmol) was added dropwise MeLi (2.80 mL, 1.6 M in Et.sub.2O, 4.40 mmol) and the resulting solution was stirred for 16 h. The volatiles were then removed in vacuo and the yellow solid was then extracted into n-hexanes (50 mL). Concentration of the solution to ca. 15 mL and subsequent storage at −30° C. for 24 h resulted in crystallisation of the desired product as large yellow crystals which were isolated and dried in vacuo. Yield=0.37 g (40%). The product was characterized by .sup.1H-NMR and .sup.13C-NMR. Cp* means η.sup.5—C.sub.5Me.sub.5.

[0141] Compound V Me.sub.5CpTiCl.sub.2(NC(2,6-C.sub.6H.sub.3F.sub.2)(.sup.iPr.sub.2N)) was prepared as described for compound 10 in WO 2005/090418

[0142] Compound VM Me.sub.5CpTiMe.sub.2(NC(2,6-C.sub.6H.sub.3F.sub.2)(.sup.iPr.sub.2N)) was prepared as described for compound 10M in WO 2005/090418

[0143] Compound W (.sup.nBuCp)TiCl.sub.2(NC(2,6-C.sub.6H.sub.3F.sub.2)(.sup.iPr.sub.2N)) was prepared as described for compound 15 in WO 2005/090418

[0144] Compound X Me.sub.5CpTiCl.sub.2(NC(C.sub.13FH.sub.9N)

[0145] To a solid mixture of (2-(2,6-difluorophenyl)-2,3-dihydro-isoindol-1-ylideneamine) (Ligand K) (4.50 g, 18.4 mmol) and Cp*TiCl.sub.3 (5.33 g, 18.4 mmol) was added toluene (100 mL) and triethylamine (11.3 mL, 46.1 mmol). The solution was stirred for two days at room temperature. The volatiles were removed under reduced pressure before the resulting orange solid was extracted into toluene (2×250 mL). Following filtration, the solutions were concentrated to 100-120 mL and stored for two days at −35° C. The yellow crystalline solid was collected by filtration and washed carefully with hexanes (3×15 mL). Yield=4.75 g (52%). .sup.1H NMR (300 MHz, C.sub.6H.sub.6, R.T.); δ 8.03-8.00 (m, 1H, CHC(C═N)), 7.04-7.01 (m, 2H, Ar), 6.71-6.69 (m, 1H, Ar), 6.65-6.63 (m, 3H, Ar), 4.05 (s, 2H, NCH.sub.2C), 1.98 (s, 15H, C.sub.5Me.sub.5) ppm. .sup.13C NMR (75 MHz, C.sub.6D.sub.6, R.T.); δ 161.89-158.46 (dd, J=253.6, 4.7 Hz, CF(Ar)), 159.74 (NC), 141.35 (Ar), 133.93 (Ar), 131.59 (Ar), 129.75-129.49 (t, J=9.8 Hz, CFCHCHCHCF(Ar)), 128.63 (Ar), 127.90 (Ar), 125.31 (Ar), 122.96 (C.sub.5Me.sub.5), 116.43 (t (very weak), N═CNCCF), 112.40-112.09 (m, CFCHCHCHCF), 53.83 (NCH.sub.2C), 13.02 (C.sub.5Me.sub.5) ppm. .sup.19F NMR (300 MHz, C.sub.6H.sub.6, R.T.); δ −115.4 ppm.

Inventive Complexes

[0146] Complex 1 (.sup.tBuCp)TiCl.sub.2(NC(Ph)(.sup.iPr.sub.2N))

[0147] To a solution of N,N-diisopropylbenzamidine (Ligand E) (0.500 g, 2.45 mmol) and .sup.yBuCpTiCl.sub.3 (0.674 g, 2.45 mmol) in toluene (30 mL), was added triethylamine (1.35 mL) and the mixture was stirred overnight at 50° C. The mixture was filtered and concentrated in vacuo, yielding the product as a bright yellow powder (0.77 g, 70.5%) .sup.1H NMR (300 MHz, CDCl.sub.3) δ: 7.50-7.16 (3H, ArH); 6.04 (2H, t, J=2.8 Hz, CpH); 5.77 (2H, t, J=2.8 Hz, CpH); 3.65 (2H, br. s., CH(CH.sub.3).sub.2); 1.63 (6H, br. s., CH(CH.sub.3).sub.2); 1.15 (9H, s, CpC(CH.sub.3).sub.3); 1.12 (6H, br. s., CH(CH.sub.3).sub.2) ppm. .sup.13C NMR (75 MHz, CDCl.sub.3) δ: 166.3, 145.3, 138.6, 129.6, 129.2, 126.2, 114.8, 114.3, 53.1, 49.1, 33.3, 31.4, 20.84 ppm.

[0148] Complex 2 (.sup.tBuCp)TiCl.sub.2(NC(2,6-C.sub.6H.sub.3F.sub.2)(.sup.iPr.sub.2N))

[0149] Prepared with 2,6-difluoro-N,N-diisopropylbenzimidamide (Ligand I) using the procedure described for Compound 1.

[0150] .sup.1H-NMR (300 MHz, CDCl3) δ: 7.37 (1H, m, J=8.6, 6.4, p-ArH); 7.09-6.97 (2H, m, m-ArH); 6.29 (2H, t, J=2.7, CpH); 6.09 (2H, t, J=2.7, CpH); 3.75 (1H, sept, J=6.8 Hz, CH(CH.sub.3).sub.2); 3.63 (1H, sept, J=6.8 Hz, CH(CH.sub.3).sub.2); 1.68 (6H, d, J=6.8 Hz, CH(CH.sub.3).sub.2); 1.26 (9H, s, CpC(CH.sub.3).sub.3); 1.20 (6H, d, J=6.8 Hz, CH(CH.sub.3).sub.2) ppm. .sup.13C-NMR (75 MHz, CDCl.sub.3) δ: 158.3 (dd, .sup.1J=250.1 Hz, .sup.3J=7.3 Hz); 154.4; 146.3; 131.1 (t, .sup.3J=9.5 Hz), 115.4 (t, .sup.2J=23.3 Hz); 115.0; 114.45; 112.7-112.2 (m); 53.7; 49.3; 33.5; 31.3; 21.0; 20.8 ppm. .sup.19F-NMR (282 MHz, CDCl.sub.3) δ: −113.1 ppm.

[0151] Complex 2M (.sup.tBuCp)TiMe.sub.2(NC(2,6-C.sub.6H.sub.3F.sub.2)(.sup.iPr.sub.2N))

[0152] Prepared with Compound 2 using the procedure described above for Compound UM.

[0153] .sup.1H-NMR (300 MHz, CDCl.sub.3) δ: 7.13 (1H, m, J=8.6 Hz, 6.4 Hz, p-ArH); 6.88-6.74 (2H, m, m-ArH); 5.82 (2H, t, J=2.7 Hz, CpH); 5.58 (2H, t, J=2.7 Hz, CpH); 3.70 (1H, sept, J=6.8 Hz, CH(CH.sub.3).sub.2); 3.62 (1H, sept, J=6.8 Hz, CH(CH.sub.3).sub.2); 1.61 (6H, d, J=6.8 Hz, CH(CH.sub.3).sub.2); 1.13 (9H, s, CpC(CH.sub.3).sub.3); 1.04 (6H, d, J=6.8 Hz, CH(CH.sub.3).sub.2); 0.10 (6H, s, Ti(CH.sub.3).sub.2) ppm.

[0154] .sup.13C-NMR (75 MHz, CDCl.sub.3) δ: 158.2 (dd, J=247.9 Hz, 8.3 Hz); 149.1; 141.1; 128.8 (t, J=9.4 Hz); 118.6 (t, J=24.3 Hz); 111.9-111.3 (m); 110.4; 107.8; 52.2; 47.5; 46.5; 32.4; 31.50; 21.1; 20.5 ppm. .sup.19F-NMR (282 MHz, CDCl.sub.3) δ: −114.7 ppm.

Part II—In Situ Catalyst Formation

[0155] Catalysts were prepared in situ by employing a combinatorial approach using either C.sub.5R.sub.5TiCl.sub.3 complexes (P and Q) and an equivalent quantity of one of the protio ligands A-K. For the in situ-generated complexes presented in Table 1, the protio ligand (A-K) was first deprotonated with one equivalent of MeMgCl (3.0M in THF) in toluene for thirty minutes at room temperature before a toluene solution of either P or Q (one molar equivalent) was added. Each combination of ligand A-K with metal precursor Q represents an invented catalyst component. The concentrations were adjusted such that the overall concentration of titanium in the final solution was 40 mM. The solutions were then employed in polymerization reactions (Part III).

Part III EPDM Co-Polymerizations Using In Situ-Generated Catalysts (Tables 1 and 2)

[0156] The polymerizations with the in situ-generated catalysts were carried out in 48 parallel pressure reactors (PPR48). The PPR reactor cells were fitted with a pre-weighed glass vial insert and a disposable stirring paddle. The reactors were sealed, tested with Nitrogen at 130 psi to ensure that leaks not higher than 0.1 psi min.sup.−1 may occur. The reactor atmosphere was then purged three times with propene at 80 psi, and 3.9 mL of toluene was added (toluene was first purified by passing through MBraun SPS mixed bed columns), along with 200 mL of an ENB/MMAO-3A/BHT toluene solution with the following composition: ENB (Sigma Aldrich, used as received, 5% v/v) 34 mM (final reactor concentration), MMAO-3A (AKZO NOBEL) 50 mM and BHT (Sigma Aldrich, used as received) 25 mM. The liquid reactants were injected into each cell through a valve. The reactors were heated at 40° C. and the cells were pressurized with 50 psi of propene (Linde Gas, further purified through Selexorb and BASF catalysts for Oxygen and moisture removal) for 5 minutes with a stirring speed of the paddles of 800 rpm. After pressure stabilization, the reactors were heated at the polymerization temperature (90° C.) and the reactors were then left to equilibrate for 20 minutes. The reactors were then pressurized with ethene until a final pressure of 130 psi was reached. The pre-catalyst and activator (Trityl Tetrakis(pentafluorophenyl)borate (TBF20)) toluene solutions (4 mM) were injected into the cells preventing contact with a 50 μL nitrogen gap in the dispensation needle. The ratio of [B]:[Ti] was set at 2. The pre-catalyst loading was adjusted such that mass transport limitations were not encountered. The polymerization was run at constant temperature and ethene partial pressure for 5 minutes, then quenched with an oxygen/nitrogen mixture (2% Oxygen content v/v) at 50 psi (3.4 bar) overpressure. The reactors were cooled, vented and purged with N.sub.2, in order to prevent the glove box pollution from the quenching gas. After purging with inert gas, the reactors were opened and the glass inserts were unloaded from the cells, transferred to the centrifuge/vacuum drying station (Genevac EZ-2 Plus) and the volatiles were removed under reduced pressure overnight. The polymer samples were then weighed on a Weighting Station unit and the polymer yields were recorded. The polymers were analysed for molecular weight (IV—calculated from Mw value (SEC-IR) with reference to a calibration line correlating Mw (SEC-IR 160° C.) and IV (Ubbelohde 135° C.), Mw/Mn and composition (FT-IR).

Part IV—Batch EPDM Co-Polymerizations (General Procedure) (Tables 3-6)

[0157] The batch co-polymerizations were carried out in a 2-liter batch autoclave equipped with a double intermig and baffles. The reaction temperature was set on 90+/−3° C. and controlled by a Lauda Thermostat. The feed streams (solvents and monomers) were purified by contacting with various adsorption media to remove catalyst killing impurities such as water, oxygen and polar compounds as is known to those skilled in the art. During polymerisation the ethylene and propylene monomers were continuously fed to the gas cap of the reactor. The pressure of the reactor was kept constant by a back-pressure valve.

[0158] In an inert atmosphere of nitrogen, the reactor was filled with pentamethylheptanes (PMH) (950 mL), MAO-10T (Crompton, 10 wt % in toluene), BHT and, for the EPDM/EPDM high ENB experiments, 5-ethylidene-2-norbonene (ENB) and/or 5-vinyl-2-norbonene (VNB). The reactor was heated to 90° C., while stirring at 1350 rpm. The reactor was pressurized and conditioned under a determined ratio of ethylene, propylene and, for the EPDM/EPDM high ENB experiments, hydrogen (0.35 NL/h). After 15 minutes, the catalyst component was added into the reactor (0.1-0.8 μmol depending on catalyst productivity) and the catalyst vessel was rinsed with PMH (50 mL) subsequently. After 10 minutes of polymerisation, the monomer flow was stopped and the solution was carefully dumped in an Erlenmeyer flask of 2 L, containing a solution of Irganox-1076 in iso-propanol and dried over night at 100° C. under reduced pressure. The polymers were analysed for intrinsic viscosity (IV) and composition (FT-IR).

[0159] The experimental conditions and results are given in tables 3 to 6.

TABLE-US-00001 TABLE 1 No. of poly- No. of Av. Av. Av Av. Av. Example Metal merisa- polymers M-cont.sup.1) C2.sup.2) ENB.sup.2) IV.sup.2) Mw/ No. Ligand Precursor tions analysed (ppm Ti) (wt. %) (wt. %) dL/g Mn.sup.2) 1 A Compound P 6 6 8.1 33.6 2.2 3.9 2.1 2 A Compound Q 6 6 9.8 33.7 8.9 3.0 2.1 3 B Compound P 6 6 3.7 27.6 4.9 2.6 2.1 4 B Compound Q 6 6 18.3 30.0 11.3 2.9 2.1 5 C Compound P 6 6 3.3 32.8 6.8 4.2 2.3 6 C Compound Q 6 6 18.6 32.6 10.3 4.1 2.1 7 D Compound P 6 6 15.4 29.2 3.2 4.2 2.3 8 D Compound Q 6 3 32.3 26.9 11.5 3.6 2.1 9 E Compound P 6 6 2.9 35.1 8.8 3.9 2.1 10 E Compound Q 6 5 7.5 34.4 13.5 2.8 2.1 11 F Compound P 5 5 2.8 36.5 4.3 3.9 2.2 12 F Compound Q 6 4 6.9 32.9 11.4 3.2 2.2 13 G Compound P 6 3 25.9 27.9 7.5 4.2 2.3 14 G Compound Q 6 6 19.7 28.8 14.0 3.2 2.1 15 H Compound P 6 6 2.2 32.5 6.0 3.3 2.1 16 H Compound Q 6 6 7.7 34.3 10.9 3.1 2.1 17 I Compound P 5 6 1.9 32.6 6.3 3.5 2.2 18 I Compound Q 6 6 4.6 33.4 10.4 3.1 2.1 19 J Compound P 6 5 3.0 32.2 5.0 3.9 2.1 20 J Compound Q 6 6 7.9 33.4 12.4 2.9 2.1 21 K Compound P 5 5 4.9 24.0 3.4 3.6 2.1 22 K Compound Q 5 5 8.0 34.0 5.4 3.2 2.1 .sup.1)Average value determined from respective number of polymerizations. .sup.2)Average value determined from number of analysed polymers.

TABLE-US-00002 TABLE 2 Metal No. of Precursor/ poly- No. of Av. Av. Av Av. Example Isolated merisa- polymers M-cont.sup.1) C2.sup.2) ENB.sup.2) IV.sup.2) No. Catalyst tions analysed (ppm Ti) (wt. %) (wt. %) dL/g 23 X 6 5 2.1 24.4 3.9 3.5 24 1 5 4 5.4 39.7 10.9 3.0 25 2 5 6 4.3 32.4 12.9 3.1 26 2M 6 6 5.7 35.4 10.2 3.1 .sup.1)Average value determined from respective number of polymerizations. .sup.2)Average value determined from number of analysed polymers.

TABLE-US-00003 TABLE 3 Exp. Example Com- Type Yield M-cont C2 C3 IV No. plex C3:C2 (gram) (ppm Ti) (wt. %) (wt. %) dL/g 27 1 80:40 2.6 1.3 56.0 43.6 7.3 28 1 50:50 10.6 0.9 67.5 32.5 8.0 29 2 80:40 2.6 1.3 49.0 51.0 6.1 30 2 50:50 5.4 0.6 63.4 36.6 7.9 31 2M 80:40 10.2 0.9 49.1 50.9 5.2 32 2M 50:50 10.3 0.5 66.7 33.3 7.4 Table 3. 90° C., 7 bar, 10 min, MAO/BHT ([BHT} = 900 μmol/L; [Al] = 450 μmol/L. EPM 50/50: 250 NL/h C.sub.3, 250 NL/h C.sub.2, EPM 80/40: 400 NL/h C.sub.3, 200 NL/h C.sub.2,

TABLE-US-00004 TABLE 4 Example Yield M-cont C2 C3 C9/ENB VNB IV No. Complex Exp. Type (gram) (ppm Ti) (wt. %) (wt. %) (wt. %) (wt. %) dL/g 33 1 EPDM 2.3 2.1 50.2 43.0 4.1 2.8 4.1 34 1 EPDM high ENB 2.3 2.1 47.5 38.3 14.3 — 3.4 35 2 EPDM 1.5 3.3 45.8 48.1 3.5 2.6 nd 36 2 EPDM high ENB 1.5 3.2 43.8 42.8 13.5 — nd 37 2M EPDM 4.3 2.3 46.0 47.9 3.8 2.4 4.7 38 2M EPDM high ENB 4.7 2.0 42.9 45.8 11.3 — 3.5 Table 4. 90° C., 7 bar, 10 min, MAO/BHT ([BHT} = 900 μmol/L; [Al] = 450 μmol/L. EPDM: 400 NL/h C.sub.3, 200 NL/h C.sub.2, 0.35 NL/h H.sub.2, 0.7 mL VNB, 0.7 mL ENB. High ENB: 400 NL/h C.sub.3, 200 NL/h C.sub.2, 0.35 NL/h H.sub.2, 2.8 mL ENB

TABLE-US-00005 TABLE 5 Compar- ative Exp. Example Com- Type Yield M-cont C2 C3 IV No. pound C3:C2 (gram) (ppm Ti) (wt. %) (wt. %) dL/g 39 T 80:40 6.1 3.1 55.1 44.9 2.3 40 T 50:50 7.3 2.6 68.9 31.1 3.1 41 UM 80:40 12.5 0.2 52.6 47.4 7.5 42 UM 50:50 17.2 0.1 63.2 36.8 8.2 43 VM 80:40 13.8 0.2 47.7 52.3 5.5 44 VM 50:50 20.2 0.1 62.0 38.0 6.3 Table 5. 90° C., 7 bar, 10 min, MAO/BHT ([BHT} = 900 μmol/L; [Al] = 450 μmol/L. EPM 50/50: 250 NL/h C.sub.3, 250 NL/h C.sub.2, EPM 80/40: 400 NL/h C.sub.3, 200 NL/h C.sub.2,

TABLE-US-00006 TABLE 6 Compar- ative Example Com- Yield M-cont C2 C3 C9/ENB VNB IV No. pound Exp. Type (gram) (ppm Ti) (wt. %) (wt. %) (wt. %) (wt. %) dL/g 45 T EPDM 1.8 8.0 48.3 44.6 4.1 3.1 nd 46 T EPDM high ENB 2.7 11 45.7 40.5 13.8 — 2.5 47 U EPDM 7.5 0.6 45.1 53.1 1.1 0.7 nd 48 V EPDM 8.5 0.6 42.0 56.2 1.1 0.7 nd 49 VM EPDM 10.6 0.6 48.0 50.2 1.1 0.8 2.7 50 VM EPDM high ENB 14.5 0.3 45.9 50.5 3.6 — nd 51 W EPDM.sup.a 3.8 3.8 42.0 53.3 2.7 2.0 nd 52 W EPDM.sup.a,b 4.8 3.0 54.0 41.2 2.7 2.1 nd Table 6. 90° C., 7 bar, 10 min, MAO/BHT ([BHT} = 900 μmol/L; [Al] = 450 μmol/L. .sup.aMAO/BHT ([BHT} = 1800 μmol/L; [Al] = 900 μmol/L. EPDM: 400 NL/h C.sub.3, 200 NL/h C.sub.2, 0.35 NL/h H.sub.2 (.sup.b250 NL/h C.sub.3, 250 NL/h, 0.35 NL/h H.sub.2), 0.7 mL VNB, 0.7 mL ENB. High ENB: 400 NL/h C.sub.3, 200 NL/h C.sub.2, 0.35 NL/h H.sub.2, 2.8 mL ENB

[0160] From Table 1, in all cases the invented catalysts derived from precursor Q, give higher ENB incorporations in combination with a given ligand (A-K) than observed for the corresponding catalysts derived from precursor P. The intrinsic viscosities (IV) are similar in most cases and higher for examples using the inventive combination of ligand B and precursor Q compared to ligand B with precursor P. The effect of the third monomer (ENB) can result in differences in molecular weight capability being less easily observed hence the additional comparison of ethylene-propylene copolymers (in the absence of a third monomer) in Tables 3 and 5. Table 2 demonstrates the similarity of polymer properties when the isolated catalysts (X, 1, 2 and 2M) are dosed compared to the corresponding in situ generated catalysts (P+K, Q+E, Q+I) shown in Table 1. Comparing the invented compounds (1, 2 and 2M) with the comparative compounds (T, UM and VM) we see from tables 3 and 5 that the intrinsic viscosity IV (a measure of the molecular weight of the polymer) is similar for the invented compounds and UM and VM. Compound T makes polymer with lower intrinsic viscosity, hence lower molecular weight and is less active than the invented compounds.

[0161] Comparing the invented compounds (1, 2 and 2M) with comparative compounds (U, V, VM and W), we see from tables 4 and 6 that the invented compounds give a superior incorporation of non-conjugated dienes (ENB) and (VNB) than the comparative compounds U, V, VM and W. The incorporation of ENB and VNB of the invented compounds is similar to compound T (but as described above compound T is less productive and is limited to producing lower molecular weight polymer).

[0162] Thus overall the invented compounds result in simultaneous capability to make high molecular weight polymer combined with high diene affinity.