Bimetallic complex comprising cyclopentadienyl and amidine ligands

Abstract

The present invention relates to a new bimetallic complex of the formula (1) wherein: M is a group 4-6 metal R.sup.1 means is a substituent comprising a heteroatom of group 15, through which R.sup.1 is bonded to the imine carbon atom; R.sup.2-R.sup.6 are the same or different and each represents a hydrogen atom, an optionally substituted C1-10 alkyl group, an optionally substituted C1-10 alkoxy group, an optionally substituted C6-20 aryl group, an optionally substituted C6-20 aryloxy group, an optionally substituted C7-20 aralkyl group, an optionally substituted C7-20 aralkyloxy group, a silyl group substituted with optionally substituted C1-20 hydrocarbon group(s), a C1-20 hydrocarbon-substituted amino group or the adjacent R.sup.2-R.sup.6 may be linked to each other to form a ring; R.sup.7-R.sup.10 are the same or different and each represents a hydrogen atom, a halogen atom, an optionally substituted C1-10 alkyl group, an optionally substituted C1-10 alkoxy group, an optionally substituted C6-20 aryl group, an optionally substituted C6-20 aryloxy group, an optionally substituted C7-20 aralkyl group, an optionally substituted C7-20 aralkyloxy group, a silyl group substituted with optionally substituted C1-20 hydrocarbon group(s), a C1-20 hydrocarbon-substituted amino group or the adjacent R.sup.7-R.sup.10 may be linked to each other to form a ring; L is an optional neutral Lewis basic ligand, and j is an integer denoting the number of neutral ligands L; and X is an anionic ligand, and r is an integer denoting the number of anionic ligands X and wherein the two cyclopentadienyl-amidinato-metal-containing moieties as in the brackets are the same or different. ##STR00001##

Claims

1. A bimetallic complex of the formula (1) ##STR00011## having two cyclopentadienyl-amidinato-metal-containing moieties as in the brackets, wherein: M is a group 4-6 metal; R.sup.1 is a substituent comprising nitrogen, through which R.sup.1 is bonded to the imine carbon atom; R.sup.2-R.sup.6 are the same or different, and each represents a hydrogen atom, an optionally substituted C1-10 alkyl group, an optionally substituted C1-10 alkoxy group, an optionally substituted C6-20 aryl group, an optionally substituted C6-20 aryloxy group, an optionally substituted C7-20 aralkyl group, an optionally substituted C7-20 aralkyloxy group, a silyl group substituted with optionally substituted C1-20 hydrocarbon group(s), a C1-20 hydrocarbon-substituted amino group, or the adjacent R.sup.2-R.sup.6 are optionally linked to each other to form a ring; R.sup.7-R.sup.10 are the same or different, and each represents a hydrogen atom, a halogen atom, an optionally substituted C1-10 alkyl group, an optionally substituted C1-10 alkoxy group, an optionally substituted C6-20 aryl group, an optionally substituted C6-20 aryloxy group, an optionally substituted C7-20 aralkyl group, an optionally substituted C7-20 aralkyloxy group, a silyl group substituted with optionally substituted C1-20 hydrocarbon group(s), a C1-20 hydrocarbon-substituted amino group, or the adjacent R.sup.7-R.sup.10 are optionally linked to each other to form a ring; L is an optional neutral Lewis basic ligand, and j is an integer denoting the number of neutral ligands L; and X is an anionic ligand, and r is an integer denoting the number of anionic ligands X, and wherein the two cyclopentadienyl-amidinato-metal-containing moieties are the same or different.

2. The bimetallic complex according to claim 1, wherein M is selected from the group consisting of Ti, Zr and Hf.

3. The bimetallic complex according to claim 1, wherein R.sup.2-R.sup.6 are the same or different and each represents a hydrogen atom or a C1-5 alkyl group.

4. The bimetallic complex according to the claim 1, wherein each X independently represents a halogen atom, a C1-10 alkyl group, a C7-20 aralkyl group, a C6-20 aryl group or a C1-20 hydrocarbon-substituted amino.

5. The bimetallic complex according to claim 1, wherein j is zero.

6. The bimetallic complex according to claim 1, wherein R.sup.7-R.sup.10 are each a hydrogen atom.

7. A process for producing the bimetallic complex represented by the formula (1) according to claim 1, the process comprising: reacting a ligand compound of the formula (2) ##STR00012## wherein R.sup.1 and R.sup.7-R.sup.10 have the same meaning as given in claim 1, with a metal compound represented by the formula (3) ##STR00013## wherein M, R.sup.2-R.sup.6, X, L and r and j have also the same meaning as given in claim 1.

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

9. The catalyst system according to claim 8, further comprising a scavenger c), wherein the scavenger c) is 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.

11. A process for the preparation of a polymer by polymerizing at least one olefinic monomer, the process comprising contacting at least one olefinic monomer with the catalyst system according to claim 8.

12. The process according to claim 11, wherein the at least one olefinic monomer comprises ethylene and at least a C.sub.3-C.sub.12--olefin.

13. The process according to claim 11, wherein the at least one olefinic monomer comprises ethylene, at least one C.sub.3-12 alpha olefin, and at least one non-conjugated diene.

14. The process according to claim 13, wherein the at least one non-conjugated diene is selected from the group consisting of 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-vinylnorbornene, 2,5-norbornadiene, dicyclopentadiene, and vinylcyclohexene.

15. The bimetallic complex according to claim 1, wherein: M is selected from the group consisting of Ti, Zr and Hf; R.sup.2-R.sup.6 are the same or different and each represents a hydrogen atom or a C1-5 alkyl group; each X independently represents a halogen atom, a C1-10 alkyl group, a C7-20 aralkyl group, a C6-20 aryl group, or a C1-20 hydrocarbon-substituted amino; j is zero; and R.sup.7-R.sup.10 are each a hydrogen atom.

16. The bimetallic complex according to claim 1, wherein: M is Ti; R.sup.2-R.sup.6 are methyl; each X independently is Cl or methyl; j is zero; and R.sup.7-R.sup.10 are each a hydrogen atom.

17. A bimetallic complex of the formula (1) ##STR00014## having two identical, or two different moieties as in the brackets, wherein: M is a group 4-6 metal; R.sup.1 is a substituent comprising a heteroatom of group 15, through which R.sup.1 is bonded to the imine carbon atom; R.sup.2-R.sup.6 are the same or different and each represents a hydrogen atom, an optionally substituted C1-10 alkyl group, an optionally substituted C1-10 alkoxy group, an optionally substituted C6-20 aryl group, an optionally substituted C6-20 aryloxy group, an optionally substituted C7-20 aralkyl group, an optionally substituted C7-20 aralkyloxy group, a silyl group substituted with optionally substituted C1-20 hydrocarbon groups), a C1-20 hydrocarbon-substituted amino group or the adjacent R.sup.2-R.sup.6 may be linked to each other to form a ring; R.sup.7-R.sup.10 are the same or different and each represents a hydrogen atom, a halogen atom, an optionally substituted C1-10 alkyl group, an optionally substituted C1-10 alkoxy group, an optionally substituted C6-20 aryl group, an optionally substituted C6-20 aryloxy group, an optionally substituted C7-20 aralkyl group, an optionally substituted C7-20 aralkyloxy group, a silyl group substituted with optionally substituted C1-20 hydrocarbon group(s), a C1-20 hydrocarbon-substituted amino group or the adjacent R.sup.7-R.sup.10 may be linked to each other to form a ring; L is an optional neutral Lewis basic ligand, and j is an integer denoting the number of neutral ligands L; and X is an anionic ligand, and r is an integer denoting the number of anionic ligands X.

Description

FIGURES

(1) FIG. 1 shows the X-ray structure of compound 1

(2) FIG. 2 shows the X-ray structure of compound 2

(3) FIG. 3 shows the X-ray structure of compound 3

(4) FIG. 4 shows the X-ray structure of compound 4

SYNTHESIS OF COMPOUNDS FOR THE COMPARATIVE EXAMPLES

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

Synthesis Me5CpTiMe2(NC(Ph)(iPr2N)) (Compound B)

(6) To a stirring toluene (15 mL) solution of Cp*Ti{NC(Ph)N.sup.iPr.sub.2}Cl.sub.2 (3) (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.

Synthesis of Compounds for the Examples of the Invention

Synthesis of 1,4-C6H4{C(NH)NiPr2}2 (Compound 1)

(7) ##STR00007##

(8) To a THF (250 mL) solution of diisopropylamine (73 mL, 0.52 mol) at 50 C. was added MeMgBr (140 mL, 3.0 M in diethyl ether, 0.42 mol). Following stirring at 50 C. for 3 h, the solution was cooled to 0 C. and 1,4-dicyanobenzene (5.38 g, 0.042 mol) was added. The solution was allowed to warm to RT and was stirred for a further 2 d. The mixture was cooled to 0 C. and quenched with methanol (50 mL) and then water (100 mL). The organic phase separated from the aqueous layer which was then back-extracted with dichloromethane (450 mL). The combined organic phases were dried over MgSO.sub.4 and the volatiles removed under reduced pressure. The off-white solid was washed with pentane (315 mL), isolated and dried in vacuo. Yield=5.32 g (38%). Diffraction-quality crystals were grown by slow evaporation from a concentrated solution of dichloromethane. .sup.1H NMR (CDCl.sub.3, 299.9 MHz, 293 K): 7.21 (4H, s, Ar), 3.59 (4H, sept, N(CHMe.sub.2).sub.2, .sup.3J=6.6 Hz), 1.29 (24H, d, N(CHMe.sub.2).sub.2, .sup.3J=6.9 Hz) ppm (NH not observed). .sup.13C{.sup.1H} NMR (CDCl.sub.3, 75.4 MHz, 293 K): 167.4 (CN(N.sup.iPr.sub.2), 141.9 (ArC(C(N.sup.iPr.sub.2)N)), 126.2 (ArCHC(C(N.sup.iPr.sub.2)N)), 48.5 (N(CHMe.sub.2).sub.2), 21.0 (N(CHMe.sub.2).sub.2) ppm. IR (NaCl plates, Nujol mull, cm.sup.1): 1576 (m, .sub.(CN)), 1225 (w), 1085 (w), 813 (w), 772 (w). ESI.sup.+-HRMS: m/z=331.2857 (calcd. for [C.sub.20H.sub.35N.sub.4].sup.+, 331.2856). Anal. found (calcd. for C.sub.20H.sub.34N.sub.4): C, 72.47 (72.68); N, 16.87 (16.95); H, 10.49 (10.37) %.

Synthesis of 1,4-C6H4{NC(NiPr2)Cp*TiMe2}2 (Compound 2)

(9) ##STR00008##

(10) To a toluene (15 mL) solution of 1,4-C.sub.6H.sub.4{C(NH)N.sup.iPr.sub.2}.sub.2 (compound 1) (1.01 g, 3.06 mmol) was added Cp*TiMe.sub.3 (1.46 g, 6.40 mmol). The brown solution was stirred for 15 h until a precipitate appeared. After filtration the yellow solid was washed with toluene (315 mL) to produce a yellow solid, which was isolated and dried in vacuo. Yield=1.18 g (51%). Diffraction-quality crystals were grown by slow cooling from a concentrated solution of hot bromobenzene. .sup.1H NMR (CDCl.sub.3, 299.9 MHz, 223 K): 7.13 (4H, s, Ar), 3.71 (2H, sept, N(CHMe.sub.2).sub.2, .sup.3J=6.9 Hz), 3.51 (2H, br, N(CHMe.sub.2).sub.2), 1.67 (12H, d, N(CHMe.sub.2).sub.2, .sup.3J=6.6 Hz), 1.64 (30H, s, C.sub.5Me.sub.5), 1.39 (12H, d, N(CHMe.sub.2).sub.2, .sup.3J=6.6 Hz), 0.19 (12H, s, TiMe) ppm. .sup.13C{.sup.1H} NMR (CDCl.sub.3, 75.4 MHz, 223 K): 160.6 (CN(N.sup.iPr.sub.2), 140.2 (ArC(C(N.sup.iPr.sub.2)N)), 125.5 (ArCHC(C(NMe.sub.2)N)), 118.9 (C.sub.5Me.sub.5), 51.8 (N(CHMe.sub.2).sub.2), 46.6 (N(CHMe.sub.2).sub.2), 45.9 (TiMe), 20.8 (N(CHMe2).sub.2), 19.9 (N(CHMe.sub.2).sub.2), 11.3 (C.sub.5Me.sub.5) ppm. IR (NaCl plates, Nujol mull, cm.sup.1): 1561 (s, .sub.(CN)), 1321 (m), 1135 (w), 890 (m), 829 (w). EI-MS: m/z=694 (3%, [M-4Me].sup.+). Anal. found (calcd. for C.sub.44H.sub.74N.sub.4Ti.sub.2): 69.85 (70.01), 9.68 (9.88), 7.57 (7.42) %.

Synthesis of 1,3-C6H4{C(NH)NiPr2}2 (Compound 3)

(11) ##STR00009##

(12) To a toluene (250 mL) solution of diisopropylamine (73 mL, 0.52 mol) at 50 C. was added MeMgBr (140 mL, 3.0 M in diethyl ether, 0.42 mol). Following stirring at 50 C. for 3 h, the solution was cooled to 0 C. and 1,3-dicyanobenzene (5.38 g, 0.042 mol) was added. The solution was refluxed for 13 h, cooled to 0 C., quenched with methanol (50 mL) and then water (100 mL). The organic phase was separated from the aqueous layer which was then back-extracted with dichloromethane (450 mL). The combined organic phases were dried over MgSO.sub.4 and the volatiles removed under reduced pressure. Yield=4.20 g (30%). Diffraction-quality crystals were grown from a concentrated pentane solution at 30 C. .sup.1H NMR (CDCl.sub.3, 299.9 MHz, 293 K): 7.39 (1H, m, ArCHCHC(C(N.sup.iPr.sub.2)N)), 7.28 (2H, m, ArCHCHC(C(N.sup.iPr.sub.2)N)), 7.19 (1H, s, ArCH(C(C(N.sup.iPr.sub.2)N)).sub.2), 5.67 (2H, br, NH), 3.65 (4H, sept, N(CHMe.sub.2).sub.2, .sup.3J=6.9 Hz), 1.37 (24H, d, N(CHMe.sub.2).sub.2, .sup.3J=6.9 Hz) ppm. .sup.13C{.sup.1H} NMR (CDCl.sub.3, 75.4 MHz, 293 K): 167.3 (CN(N.sup.iPr.sub.2), 141.5 (ArC(C(N.sup.iPr.sub.2)N)), 128.7 (ArCHCHC(C(N.sup.iPr.sub.2)N)), 125.5 (ArCHCHC(C(N.sup.iPr.sub.2)N)), 123.4 (ArCH(C(C(N.sup.iPr.sub.2)N)).sub.2), 48.3 (N(CHMe.sub.2).sub.2), 20.8 (N(CHMe.sub.2).sub.2) ppm. IR (NaCl plates, Nujol mull, cm.sup.1): 1577 (s, .sub.(CN)), 1363 (m), 1217 (m), 1027 (m), 783 (m). ESI.sup.+-HRMS: m/z=331.2853 (calcd. or [C.sub.20H.sub.35N.sub.4].sup.+, 331.2856). Anal. found (calcd. for C.sub.20H.sub.34N.sub.4): C, 72.48 (72.68); N, 16.82 (16.95); H, 10.53 (10.37) %.

Synthesis of 1,3-C6H4{NC(NiPr2)Cp*TiMe2}2 (Compound 4)

(13) ##STR00010##

(14) To a toluene (15 mL) solution of 1,3-C.sub.6H.sub.4{C(NH)N.sup.iPr.sub.2}.sub.2 (compound 3) (0.50 g, 1.5 mmol) was added Cp*TiMe.sub.3 (0.73 g, 3.2 mmol). The brown solution was stirred for 30 h. The volatiles were removed in vacuo to afford a yellow solid which was washed with pentane (315 mL) and dried in vacuo. Yield=0.52 g (46%). Diffraction-quality crystals were grown from a concentrated pentane solution at 30 C. .sup.1H NMR (CDCl.sub.3, 299.9 MHz, 223 K): 7.24 (1H, t, ArCHCHC(C(N.sup.iPr.sub.2)N).sup.3J=7.2 Hz), 7.12 (1H, s, ArCH(C(C(N.sup.iPr.sub.2)N)).sub.2), 7.07 (2H, d, ArCHCHC(C(N.sup.iPr.sub.2)N), .sup.3J=7.5 Hz), 3.77 (2H, sept, N(CHMe.sub.2).sub.2, .sup.3J=6.4 Hz), 3.50 (2H, br, N(CHMe.sub.2).sub.2), 1.73 (6H, d, N(CHMe.sub.2).sub.2, .sup.3J=6.4 Hz), 1.70 (30H, s, C.sub.5Me.sub.5), 1.56 (6H, d, N(CHMe.sub.2).sub.2, .sup.3J=6.4 Hz), 1.18 (6H, d, N(CHMe.sub.2).sub.2, .sup.3J=6.4 Hz), 1.13 (6H, d, N(CHMe.sub.2).sub.2, .sup.3J=6.4 Hz), 0.16 (12H, TiMe) ppm. .sup.13C{.sup.1H} NMR (CDCl.sub.3, 75.4 MHz, 223 K): 160.2 (CN(N.sup.iPr.sub.2), 141.5 (ArC(C(N.sup.iPr.sub.2)N)), 127.6 (ArCHCHC(C(N.sup.iPr.sub.2)N)), 124.8 (ArCHCHC(C(N.sup.iPr.sub.2)N)), 123.7 (ArCH(C(C(N.sup.iPr.sub.2)N)).sub.2), 119.1 (C.sub.5Me.sub.5), 51.9 (N(CHMe.sub.2).sub.2), 48.1 (TiMe), 46.9 (N(CHMe.sub.2).sub.2), 45.1 (TiMe.sub.2), 21.7 (N(CHMe.sub.2).sub.2), 20.9 (N(CHMe.sub.2).sub.2), 20.2 (N(CHMe.sub.2).sub.2), 20.0 (N(CHMe.sub.2).sub.2) 11.7 (C.sub.5Me.sub.5) ppm. IR (NaCl plates, Nujol mull, cm.sup.1): 1549 (s, CN), 1320 (m), 1036 (m), 688 (w). EI-MS: m/z=724 (25%, [M-2Me].sup.+). Anal. found (calcd. for C.sub.44H.sub.74N.sub.4Ti.sub.2): 69.65 (70.01), 9.84 (9.88), 7.42 (7.42) %.

Part IIBatch EPDM Terpolymerisations (General Procedure)

(15) The batch copolymerizations 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.

(16) In an inert atmosphere of nitrogen, the reactor was filled with PMH (950 mL), MAO-10T (Crompton, 10 wt % in toluene) (450 mol/L), BHT (900 mol/L), 5-ethylidene-2-norbonene (ENB) (0.7 mL) and 5-vinyl-2-norbonene (VNB) (0.7 mL). 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 hydrogen (0.35 NL/h) After 15 minutes, the catalyst components (0.1 mol) were added into the reactor 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), for molecular weight distribution (SEC-DV) and composition (FT-IR).

(17) The level of long chain branching of the polymers was determined using Dynamic Mechanical Spectrometry (DMS) experiments and expressed by the so-called delta-delta value () which is used as a measure of the non-Newtonian viscoelastic behaviour of EPDM polymers. The parameter is defined as the difference between the phase angle, , at frequencies of 10.sup.1 rad/s and 10.sup.2 rad/s as derived from frequency sweep plots obtained in a DMS experiment at 125 C. The presence of branched polymer chains will decrease the value specifically at low frequencies while the the value at high frequencies is dependent primarily of the average molecular weight of the polymer. As a result the value decreases with increasing long chain branching.

(18) The experimental results are given in table 1

(19) TABLE-US-00001 TABLE 1 Metal- Incorpo- Exam- organic Yield rated C2 ENB VNB IV Mw Mz Mw/ ple Compound (g) (wt %) (wt %) (wt %) (dl/g) (kg/mol) (kg/mol) Mn / 1 2 11.95 42.5 0.69 0.43 2.0 195 480 2.6 46.0 2 2 11.81 47.7 0.71 0.44 2.3 44.1 3 4 3.40 47.7 0.68 0.43 2.3 205 410 2.4 45.7 4 4 2.77 45.1 0.63 0.41 2.1 45.9 5 B 8.02 49.6 1.07 0.74 2.8 275 565 2.4 42.0 6 B 7.66 47.5 1.04 0.74 2.7 43.3
C3 feed=400 NL/h; C2 feed=200 NL/h; ENB feed=0.7 ml; VNB feed=0.7 ml; H2 feed=0.35 NL/h; T=90 C.; P=7 barg

(20) The conditions of the polymerization were designed to minimize long chain branching effects in each case maximizing the capability of each catalyst to produce polymer with as little branching as possible. The table shows that very similar polymer properties (C2 incorporation, polymer molecular weight, PDI). The DMS () measurements observed for compounds 2, 4 and B revealed higher values for the invented catalysts (2 and 4) compared to catalyst B meaning less long chain branching evident in the invented catalysts 2 and 4 compared to catalyst B.