CATALYSTS

Abstract

Novel catalytic compositions are disclosed comprising novel unsymmetrical metallocene catalytic compounds. Also disclosed are uses of such catalytic compositions in olefin polymerisation reactions, as well as processes of polymerising olefins. When compared with the prior art compositions, the catalytic compositions of the invention are markedly more active in the polymerisation of olefins.

Claims

1. A composition comprising a solid methyl aluminoxane support material and compound of the formula (I) shown below: ##STR00031## wherein: R.sub.1 and R.sub.2 are each independently (1-2C)alkyl; R.sub.3 and R.sub.4 are each independently hydrogen or (1-4C)alkyl, or R.sub.3 and R.sub.4, taken together with the atoms to which they are attached, form a 6-membered fused aromatic ring optionally substituted with one or more groups selected from the group consisting of (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, aryl, heteroaryl, carbocyclic and heterocyclic, wherein each aryl, heteroaryl, carbocyclic and heterocyclic group is optionally substituted with one or more groups selected from the group consisting of (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, halo, amino, nitro, cyano, (1-6C)alkylamino, [(1-6C)alkyl].sub.2amino and —S(O).sub.2(1-6C)alkyl; R.sub.5 and R.sub.6 are each independently hydrogen or (1-4C)alkyl, or R.sub.5 and R.sub.6, taken together with the atoms to which they are attached, form a 6-membered fused aromatic ring optionally substituted with one or more groups selected from the group consisting of (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, aryl, heteroaryl, carbocyclic and heterocyclic, wherein each aryl, heteroaryl, carbocyclic and heterocyclic group is optionally substituted with one or more groups selected from the group consisting of (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, halo, amino, nitro, cyano, (1-6C)alkylamino, [(1-6C)alkyl].sub.2amino and —S(O).sub.2(1-6C)alkyl; Q is a bridging group comprising 1, 2 or 3 bridging atoms selected from the group consisting of C, N, O, S, Ge, Sn, P, B, and Si, or a combination thereof, and is optionally substituted with one or more groups selected from the group consisting of hydroxyl, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy and aryl; X is zirconium, titanium or hafnium; and each Y group is independently selected from the group consisting of halo, hydrogen, a phosphonate anion, a sulfonate anion, a borate anion, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, aryl, and aryloxy, wherein each of (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, aryl, and aryloxy is optionally substituted with one or more groups selected from the group consisting of (1-6C)alkyl, halo, nitro, amino, phenyl, (1-6C)alkoxy, —C(O)NR.sub.xR.sub.y and Si[(1-4C)alkyl].sub.3; wherein R.sub.x and R.sub.y are independently (1-4C)alkyl; with the proviso that: when R.sub.3 and R.sub.4 are hydrogen or (1-4C)alkyl, R.sub.5 and R.sub.6 are not linked to form a fused 6-membered aromatic ring that is substituted with four methyl groups; and when R.sub.5 and R.sub.6 are hydrogen or (1-4C)alkyl, R.sub.3 and R.sub.4 are not linked to form a fused 6-membered aromatic ring that is substituted with four methyl groups.

2. The composition according to claim 1, wherein R.sub.3 and R.sub.4 are each independently hydrogen or (1-4C)alkyl, or R.sub.3 and R.sub.4, taken together with the atoms to which they are attached, form a fused 6-membered aromatic ring optionally substituted with one or more groups selected from the group consisting of (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)alkoxy, aryl, heteroaryl, carbocyclic and heterocyclic, wherein each aryl, heteroaryl, carbocyclic and heterocyclic group is optionally substituted with one or more groups selected from the group consisting of (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)alkoxy, halo, amino, nitro, cyano, (1-4C)alkylamino, [(1-4C)alkyl].sub.2amino and —S(O).sub.2(1-4C)alkyl; and R.sub.5 and R.sub.6 are each independently hydrogen or (1-4C)alkyl, or R.sub.5 an R.sub.6, taken together with the atoms to which they are attached, form a fused 6-membered aromatic ring optionally substituted with one or more groups selected from the group consisting of (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)alkoxy, aryl, heteroaryl, carbocyclic and heterocyclic, wherein each aryl, heteroaryl, carbocyclic and heterocyclic group is optionally substituted with one or more groups selected from the group consisting of (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)alkoxy, halo, amino, nitro, cyano, (1-4C)alkylamino, [(1-4C)alkyl].sub.2amino and —S(O).sub.2(1-4C)alkyl.

3. The composition according to claim 1, wherein R.sub.3 and R.sub.4 are each independently hydrogen or (1-4C)alkyl, or R.sub.3 and R.sub.4, taken together with the atoms to which they are attached, form a fused 6-membered aromatic ring optionally substituted with one or more groups selected from the group consisting of (1-4C)alkyl, aryl, heteroaryl, carbocyclic and heterocyclic, wherein each aryl, heteroaryl, carbocyclic and heterocyclic group is optionally substituted with one or more groups selected from the group consisting of (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)alkoxy, halo, amino and nitro; and R.sub.5 and R.sub.6 are each independently hydrogen or (1-4C)alkyl, or R.sub.5 and R.sub.6, taken together with the atoms to which they are attached, form a fused 6-membered aromatic ring optionally substituted with one or more groups selected from the group consisting of (1-4C)alkyl, aryl, heteroaryl, carbocyclic and heterocyclic, wherein each aryl, heteroaryl, carbocyclic and heterocyclic group is optionally substituted with one or more groups selected from the group consisting of (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)alkoxy, halo, amino and nitro.

4. (canceled)

5. The composition according to claim 1, wherein R.sub.3 and R.sub.4 are each independently hydrogen or (1-4C)alkyl, or R.sub.3 and R.sub.4, taken together with the atoms to which they are attached, form a fused 6-membered aromatic ring optionally substituted with one or more groups selected from the group consisting of (1-4C)alkyl and phenyl, wherein each phenyl group is optionally substituted with one or more groups selected from the group consisting of (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)alkoxy, halo, amino and nitro; and R.sub.5 and R.sub.6 are each independently hydrogen or (1-4C)alkyl, or R.sub.5 and R.sub.6, taken together with the atoms to which they are attached, form a fused 6-membered aromatic ring optionally substituted with one or more groups selected from the group consisting of (1-4C)alkyl and phenyl, wherein each phenyl group is optionally substituted with one or more groups selected from the group consisting of (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)alkoxy, halo, amino and nitro.

6. The composition according to claim 1, wherein: when R.sub.3 and R.sub.4 are hydrogen or (1-4C)alkyl, and R.sub.5 and R.sub.6 are taken together with the carbon atoms to which they are attached to form a fused 6-membered aromatic ring, said ring is optionally substituted with one or two substituents selected from the group consisting of (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, halo, amino, nitro, cyano, (1-6C)alkylamino, [(1-6C)alkyl].sub.2amino and —S(O).sub.2(1-6C)alkyl; or when R.sub.5 and R.sub.6 are hydrogen or (1-4C)alkyl, and R.sub.3 and R.sub.4 are taken together with the carbon atoms to which they are attached to form a fused 6-membered aromatic ring, said ring is optionally substituted with one or two substituents selected from the group consisting of (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, halo, amino, nitro, cyano, (1-6C)alkylamino, [(1-6C)alkyl].sub.2amino and —S(O).sub.2(1-6C)alkyl.

7. The composition according to claim 1, wherein Q is a bridging group comprising 1, 2 or 3 bridging atoms selected from the group consisting of C, and Si, or a combination thereof, and is optionally substituted with one or more groups selected from hydroxyl, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy and aryl.

8. The composition according to claim 7, wherein Q is a bridging group selected from —[C(R.sub.a)(R.sub.b)—C(R.sub.c)(R.sub.d)]— and —[Si(R.sub.e)(R.sub.f)]—, wherein R.sub.a, R.sub.b, R.sub.c, R.sub.d, R.sub.e and R.sub.f are independently selected from hydrogen, hydroxyl, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy and aryl.

9. The composition according to claim 8, wherein R.sub.a, R.sub.b, R.sub.c and R.sub.d are each hydrogen, and R.sub.e and R.sub.f are each independently (1-6C)alkyl, (2-6C)alkenyl or phenyl.

10. The composition according to claim 8, wherein Q is a bridging group —[Si(R.sub.e)(R.sub.f)]—, wherein R.sub.e and R.sub.f are each independently methyl, ethyl, propyl, i-propyl, allyl or phenyl.

11. The composition according to claim 1, wherein each Y is independently selected from halo or a (1-2C)alkyl group which is optionally substituted with halo, phenyl, or Si[(1-4C)alkyl].sub.3.

12. The composition according to claim 11, wherein Y is halo.

13. The composition according to claim 1, wherein X is zirconium or hafnium.

14. (canceled)

15. The composition according to claim 1, wherein the compound of formula (I) has any of formulae (II), (III) or (IV): ##STR00032## wherein: R.sub.1 and R.sub.2 are each independently (1-2C)alkyl; R.sub.3 and R.sub.4 are each independently hydrogen or (1-4C)alkyl, or R.sub.3 and R.sub.4, taken together with the atoms to which they are attached, form a 6-membered fused aromatic ring optionally substituted with one or more groups selected from the group consisting of (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, aryl, heteroaryl, carbocyclic and heterocyclic, wherein each aryl, heteroaryl, carbocyclic and heterocyclic group is optionally substituted with one or more groups selected from the group consisting of (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, halo, amino, nitro, cyano, (1-6C)alkylamino, [(1-6C)alkyl].sub.2amino and —S(O).sub.2(1-6C)alkyl; R.sub.5 and R.sub.6 are hydrogen; Q is a bridging group comprising 1, 2 or 3 bridging atoms selected from the group consisting of C, N, O, S, Ge, Sn, P, B, and Si, or a combination thereof, and is optionally substituted with one or more groups selected from the group consisting of hydroxyl, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy and aryl; X is zirconium, titanium or hafnium; and each Y group is independently selected from the group consisting of halo, hydride, a phosphonate anion, a sulfonate anion, a borate anion, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, aryl, and aryloxy, wherein each of (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, aryl, and aryloxy is optionally substituted with one or more groups selected from the group consisting of (1-6C)alkyl, halo, nitro, amino, phenyl, (1-6C)alkoxy, —C(O)NR.sub.xR.sub.y and Si[(1-4C)alkyl].sub.3; wherein R.sub.x and R.sub.y are independently (1-4C)alkyl; each R.sub.7, R.sub.8 and R.sub.9 is independently selected from the group consisting of (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, halo, amino, nitro, cyano, (1-6C)alkylamino, [(1-6C)alkyl].sub.2amino and —S(O).sub.2(1-6C)alkyl; and n, m and o are independently 0, 1 or 2.

16. The composition according to claim 15, wherein each R.sub.7, R.sub.8 and R.sub.9 is independently selected from (1-4C)alkyl and phenyl, said phenyl group being optionally substituted with one or more groups selected from the group consisting of hydrogen, (1-4C)alkyl, (2-4C)alkenyl, (2-4C)alkynyl, (1-4C)alkoxy, halo, amino and nitro.

17. The composition according to claim 16 wherein each R.sub.7, R.sub.8 and R.sub.9 is independently selected from hydrogen, methyl, n-butyl, tert-butyl and phenyl.

18. The composition according to claim 1, wherein the compound of formula (I) has any of formulae (V), (VI) or (VII): ##STR00033## wherein R.sub.1 and R.sub.2 are each independently (1-2C)alkyl; R.sub.3 is hydrogen or (1-4C)alkyl; R.sub.4 is hydrogen; R.sub.5 and R.sub.6 are hydrogen or (1-4C)alkyl, or R.sub.5 and R.sub.6, taken together with the atoms to which they are attached, form a 6-membered fused aromatic ring optionally substituted with one or more groups selected from the group consisting of (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, aryl, heteroaryl, carbocyclic and heterocyclic, wherein each aryl, heteroaryl, carbocyclic and heterocyclic group is optionally substituted with one or more groups selected from the group consisting of (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, halo, amino, nitro, cyano, (1-6C)alkylamino, [(1-6C)alkyl].sub.2amino and —S(O).sub.2(1-6C)alkyl; Q is a bridging group comprising 1, 2 or 3 bridging atoms selected from the group consisting of C, N, O, S, Ge, Sn, P, B, and Si, or a combination thereof, and is optionally substituted with one or more groups selected from the group consisting of hydroxyl, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy and aryl; X is zirconium, titanium or hafnium; and each Y group is independently selected from the group consisting of halo, hydride, a phosphonate anion, a sulfonate anion, a borate anion, (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, aryl, and aryloxy, wherein each of (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, aryl, and aryloxy is optionally substituted with one or more groups selected from the group consisting of (1-6C)alkyl, halo, nitro, amino, phenyl, (1-6C)alkoxy, —C(O)NR.sub.xR.sub.y and Si[(1-4C)alkyl].sub.3; wherein R.sub.x and R.sub.y are independently (1-4C)alkyl; R.sub.7, R.sub.8 and R.sub.9 are each independently selected from the group consisting of (1-6C)alkyl, (2-6C)alkenyl, (2-6C)alkynyl, (1-6C)alkoxy, halo, amino, nitro, cyano, (1-6C)alkylamino, [(1-6C)alkyl].sub.2amino and —S(O).sub.2(1-6C)alkyl.

19. The composition according to claim 1, where the compound of formula (I) has any one of the structures shown below: ##STR00034## ##STR00035##

20. The composition according to claim 1, wherein the composition further comprises a suitable activator.

21. (canceled)

22. The composition according to claim 20, wherein the activator is methylaluminoxane (MAO), triisobutylaluminium (TIBA), diethylaluminium (DEAC) or triethylaluminium (TEA).

23. A process for preparing a polyolefin comprising contacting a composition as defined in claim 1 with one or more olefin monomers to provide a homopolymer or a copolymer.

24. The process according to claim 23, wherein the copolymer comprises 1-10 wt % of a (4-8C) α-olefin.

25. (canceled)

26. The process according to claim 23, wherein the process is performed at a temperature of 25-100° C.

27. (canceled)

Description

EXAMPLES

[0162] Examples of the invention will now be described, for the purpose of reference and illustration only, with reference to the accompanying figures, in which:

[0163] FIG. 1 shows the .sup.1H NMR spectroscopy (chloroform-d.sub.1, 298 K, 400 MHz) of pro-ligand [EB(.sup.tBu.sup.2Flu,I*)H.sub.2].

[0164] FIG. 2 shows the .sup.1H NMR spectroscopy (chloroform-d.sub.1, 298 K, 400 MHz) of pro-ligand [.sup.Me.sup.2Si(Ind*)Cl].

[0165] FIG. 3 shows the .sup.1H NMR spectroscopy (chloroform-d.sub.1, 298 K, 400 MHz) of pro-ligand [.sup.iPr.sup.2Si(Ind*)Cl].

[0166] FIG. 4 shows the .sup.1H NMR spectroscopy (chloroform-d.sub.1, 298 K, 400 MHz) of pro-ligand [.sup.Me,PropylSi(Ind*)Cl].

[0167] FIG. 5 shows the .sup.1H NMR spectroscopy (chloroform-d.sub.1, 298 K, 400 MHz) of pro-ligand [SB(Flu,I*)H.sub.2].

[0168] FIG. 6 shows the Molecular structure of [SB(.sup.tBu.sup.2Flu,I*)H.sub.2], 50% ellipsoids, hydrogen atoms omitted for clarity; black: carbon, pink: silicon. Selected bond lengths (A) and angle (1, Si-CH.sub.3 1.863 (3), 1.868(3), Si-CH.sub.Ind: 1.939(2), Si-CH.sub.Ind: 1.926(2) and HC.sub.Flu-Si-CH.sub.Ind: 111.34(12).

[0169] FIG. 7 shows the .sup.1H NMR spectroscopy (chloroform-d.sub.1, 298 K, 400 MHz) of [SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2].

[0170] FIG. 8 shows the .sup.1H NMR spectroscopy (chloroform-d.sub.1, 298 K, 400 MHz) of [SB(.sup.tBu.sup.2Flu,I*)HfCl.sub.2].

[0171] FIG. 9 shows the molecular structure of [SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2].

[0172] FIG. 10 shows the molecular structure of [SB(.sup.tBu.sup.2Flu,I*)HfCl.sub.2].

[0173] FIG. 11 shows polymerisation productivity (Kg(PE)g(Cat).sup.−1h.sup.−1) vs time (sec) for the homopolymerisation of ethylene using Solid MAO supported catalytic systems: (a) rac-[(EBI*)ZrCl.sub.2], (b) meso-[(EBI*)ZrCl.sub.2], (c) rac-[(SBI*)ZrCl.sub.2], and (d) [SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2]. Polymerisation conditions: 5 mL heptane, P.sub.ethylene=120 psi, T=70° C. and n.sub.(TEA)=10 μmol.

[0174] FIG. 12 shows polymerisation productivity (Kg(PE)g(Cat).sup.−1h.sup.−1) vs time (sec) for the homopolymerisation of ethylene using Solid MAO supported catalytic systems: (a) rac-[(EBI*)ZrCl.sub.2], (b) meso-[(EBI*)ZrCl.sub.2], (c) rac-[(SBI*)ZrCl.sub.2], and (d) [SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2]. Polymerisation conditions: 5 mL heptane, P.sub.ethylene=120 psi, T=80° C. and n.sub.(TEA)=10 μmol.

[0175] FIG. 13 shows activity vs time for the copolymerisation of ethylene and 1-hexene using Solid MAO supported catalytic systems: (a) rac-[(EBI*)ZrCl.sub.2], (b) meso-[(EBI*)ZrCl.sub.2] (c) rac-[(SBI*)ZrCl.sub.2], (d) [SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2]. Polymerisation conditions: 5 mL heptane, P.sub.ethylene=120 psi, T=70° C., [Hexene]feed=5 vol %, and n.sub.(TEA)=15 μmol.

[0176] FIG. 14 shows activity vs time for the copolymerisation of ethylene and 1-hexene using Solid MAO supported catalytic systems with variation of the 1-hexene feed. Polymerisation conditions: 5 mL heptane, P.sub.ethylene=120 psi, T=70° C., and n.sub.(TEA)=15 μmol.

[0177] FIG. 15 shows activity vs time for the copolymerisation of ethylene and 1-hexene using Solid MAO supported catalytic systems with variation of the 1-hexene feed. Polymerisation conditions: 5 mL heptane, P.sub.ethylene=80 psi, T=70° C., and n.sub.(TEA)=15 μmol.

[0178] FIG. 16 shows the molecular structure of .sup.Et2SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2.

[0179] FIG. 17 shows the molecular structure of .sup.Me,PropSB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2.

[0180] FIG. 18 shows the molecular structure of SB(.sup.tBu.sup.2Flu,I*.sup.3-ethyl)ZrCl.sub.2.

[0181] FIG. 19 shows the molecular structure of SB(Cp,I*)ZrCl.sub.2. FIG. 20 shows

[0182] FIG. 20 shows the molecular structure of SB(Cp,I*)HfCl.sub.2.

[0183] FIG. 21 shows the molecular structure of SB(Cp,I*)ZrCl(O-2,6-Me.sub.2-C.sub.6H.sub.3).

[0184] FIG. 22 shows the .sup.1H NMR spectroscopy (chloroform-d.sub.1, 298 K, 400 MHz) of .sup.Et2SB(.sup.tBu.sup.2Flu,I*)ZrC1.sub.2.

[0185] FIG. 23 shows the .sup.1H NMR spectroscopy (chloroform-d.sub.1, 298 K, 400 MHz) of .sup.Me,PropSB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2.

[0186] FIG. 24 shows the .sup.1H NMR spectroscopy (chloroform-d.sub.1, 298 K, 400 MHz) of SB(.sup.tBu.sup.2Flu,I*.sup.,3-ethyl)ZrCl.sub.2.

[0187] FIG. 25 shows the .sup.1H NMR spectroscopy (chloroform-d.sub.1, 298 K, 400 MHz) of SB(Cp,I*)ZrCl.sub.2.

[0188] FIG. 26 shows the .sup.1H NMR spectroscopy (chloroform-d.sub.1, 298 K, 400 MHz) of SB(Cp,I*)HfCl.sub.2.

[0189] FIG. 27 shows the .sup.1H NMR spectroscopy (chloroform-d.sub.1, 298 K, 400 MHz) of SB(Cp,I*)ZrCl(O-2,6-Me.sub.2-C.sub.6H.sub.3).

[0190] FIG. 28 shows activity vs time of polymerisation of ethylene using solid MAO supported/SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2 (square), solid MAO supported/SB(.sup.tBu.sup.2Flu,I*.sup.,3-Ethyl)ZrCl.sub.2 (circle), solid MAO supported/.sup.Et2SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2 (triangle), solid MAO supported/SB(Cp,I*)ZrCl.sub.2 (inverted triangle) and solid MAO supported/.sup.Me,ProPSB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2 (diamond). Polymerisation conditions: 10 mg of catalyst, 50 mL hexanes, 2 bar, 70° C., and [TIBA].sub.0/[Zr].sub.0=1000.

[0191] FIG. 29 shows activity vs temperature of polymerisation of ethylene using solid MAO supported/SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2 (square), solid MAO supported/SB(.sup.tBu.sup.2Flu,I*.sup.,3-Ethyl)ZrCl.sub.2 (circle), solid MAO supported/.sup.Et2SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2 (triangle), solid MAO supported/SB(Cp,I*)ZrCl.sub.2 (inverted triangle) and solid MAO supported/.sup.Me,PropSB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2 (diamond). Polymerisation conditions: 10 mg of catalyst, 50 mL hexanes, 2 bar, 0.5 h, and [TIBA].sub.0/[Zr].sub.0=1000.

[0192] FIG. 30 shows activity vs time of polymerisation of ethylene using solid MAO supported/SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2 (square) and solid MAO supported/SB(Cp,I*)ZrCl.sub.2 (circle). Polymerisation conditions: 10 mg of catalyst, 50 mL hexanes, 2 bar, 70° C., and [TIBA].sub.0/[Zr].sub.0=1000.

[0193] FIG. 31 shows SEM pictures of a) solid MAO supported/.sup.Et2SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2, b) solid MAO supported/.sup.Me,PropSB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2, c) solid MAO supported SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2, d) solid MAO supported SB(.sup.tBu.sup.2Flu,I*)HfCl.sub.2, e) solid MAO supported/SB(Cp,I*)ZrCl.sub.2 and f) solid MAO supported/SB(.sup.tBu.sup.2Flu,I*.sup.,3-Ethyl)ZrCl.sub.2. Polymerisation conditions: 10 mg of catalyst, 50 mL hexanes, 2 bar, 70° C., 0.5 h and [TIBA].sub.0/[Zr].sub.0=1000.

[0194] FIG. 32 shows activity vs time of polymerisation of ethylene using 3% H.sub.2 used as co-feed using solid MAO supported/SB(Cp,I*)ZrCl.sub.2, solid MAO supported/(.sup.nBuCp).sub.2ZrCl.sub.2 and solid MAO supported/(Ind).sub.2ZrCl.sub.2. Polymerisation conditions: 25 mg of catalyst, 1000 mL hexanes, 8 bar, 80° C., and [TEA].sub.0/[Zr].sub.0=300.

[0195] FIG. 33 shows activity and molecular weight vs H.sub.2 content used as co-feed using solid MAO supported/SB(Cp,I*)ZrCl.sub.2. Polymerisation conditions: 0.05 mg of catalyst, 5 mL heptane, 8 bar and 80° C.

[0196] FIG. 34 shows activity and molecular weight vs H.sub.2 content as co-feed using solid MAO supported/SB(Cp,I*)ZrCl.sub.2. Polymerisation conditions: 25 mg of catalyst, 1000 mL hexanes, 8 bar, 80° C., and [TEA].sub.0/[Zr].sub.0=300.

[0197] FIG. 35 shows activity of homopolymerisation of ethylene and copolymerisation of ethylene and 1-hexene using solid MAO supported/.sup.Et2SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2, solid MAO supported/SB(Cp,I*)ZrCl.sub.2, solid MAO supported/.sup.Me,PropSB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2, solid MAO supported SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2, solid MAO supported/SB(.sup.tBu.sup.2Flu,I*.sup.,3-Ethyl)ZrCl.sub.2, solid MAO supported SB(.sup.tBu.sup.2Flu,I*)HfCl.sub.2, and solid MAO supported/SB(Cp,I*)HfCl.sub.2. Polymerisation conditions: 0.05 mg of catalyst, 5 mL heptane, 8 bar and 80° C.

NOMENCLATURE

[0198] The nomenclature used herein will be readily understood by the skilled person having regard to the relevant structural formulae. Various abbreviations used throughout are expanded below:

SB means (Me).sub.2Si-bridged. Similarly, .sup.Et2SB means (Et).sub.2Si-bridged
EB means ethylene-bridged
Ind* or I* means per-methyl indenyl
Flu means fluorenyl
tBu means tert-butyl
Me means methyl
Pr means propyl
iPr means isopropyl
Ph means phenyl

General Methodology

[0199] All organometallic manipulations were performed under an atmosphere of N.sub.2 using standard Schlenk line techniques or a MBraun UNIlab glovebox, unless stated otherwise. All organic reactions were carried out under air unless stated otherwise. Solvents used were dried by either reflux over sodium-benzophenone diketyl (THF), or passage through activated alumina (hexane, Et.sub.2O, toluene, CH.sub.2Cl.sub.2) using a MBraun SPS-800 solvent system. Solvents were stored in dried glass ampoules, and thoroughly degassed bypassage of a stream of N.sub.2 gas through the liquid and tested with a standard sodium-benzophenone-THF solution before use. Deuterated solvents for NMR spectroscopy of oxygen or moisture sensitive materials were treated as follows: C.sub.6D.sub.6 was freeze-pump-thaw degassed and dried over a K mirror; d.sup.5-pyridine and CDCl.sub.3 were dried by reflux over calcium hydride and purified by trap-to-trap distillation; and CD.sub.2Cl.sub.2 was dried over 3 Å molecular sieves.

[0200] .sup.1H and .sup.13C NMR spectroscopy were performed using a Varian 300 MHz spectrometer and recorded at 300 K unless stated otherwise. .sup.1H and .sup.13C NMR spectra were referenced via the residual protio solvent peak. Oxygen or moisture sensitive samples were prepared using dried and degassed solvents under an inert atmosphere in a glovebox, and were sealed in Wilmad 5 mm 505-PS-7 tubes fitted with Young's type concentric stopcocks.

[0201] Mass spectra were using a Bruker FT-ICR-MS Apex III spectrometer.

[0202] For Single-crystal X-ray diffraction in each case, a typical crystal was mounted on a glass fibre using the oil drop technique, with perfluoropolyether oil and cooled rapidly to 150 K in a stream of N.sub.2 using an Oxford Cryosystems Cryostream.sup.1. Diffraction data were measured using an Enraf-Nonius KappaCCD diffractometer (graphite-monochromated MoKα radiation, λ=0.71073 Å). Series of ω-scans were generally performed to provide sufficient data in each case to a maximum resolution of 0.77 Å. Data collection and cell refinement were carried out using DENZO-SMN.sup.2. Intensity data were processed and corrected for absorption effects by the multi-scan method, based on multiple scans of identical and Laue equivalent reflections using SCALEPACK (within DENZO-SMN). Structure solution was carried out with direct methods using the program SIR92.sup.3. within the CRYSTALS software suite.sup.4. In general, coordinates and anisotropic displacement parameters of all non-hydrogen atoms were refined freely except where this was not possible due to the presence of disorder. Hydrogen atoms were generally visible in the difference map and were treated in the usual manner.sup.5.

[0203] High temperature gel permeation chromatography were performed using a Polymer Laboratories GPC220 instrument, with one PLgel Olexis guard plus two Olexis 30 cm×13 μm columns. The solvent used was 1,2,4-trichlorobenzene with anti-oxidant, at a nominal flow rate of 1.0 mLmin.sup.−1 and nominal temperature of 160° C. Refractive index and Viscotek differential pressure detectors were used. The data were collected and analysed using Polymer Laboratories “Cirrus” software. A single solution of each sample was prepared by adding 15 mL of solvent to 15 mg of sample and heating at 190° C. for 20 minutes, with shaking to dissolve. The sample solutions were filtered through a glass-fibre filter and part of the filtered solutions were then transferred to glass sample vials. After an initial delay of 30 minutes in a heated sample compartment to allow the sample to equilibrate thermally, injection of part of the contents of each vial was carried out automatically. The samples appeared to be completely soluble and there were no problems with either the filtration or the chromatography of the solutions. The GPC system was calibrated with Polymer Laboratories polystyrene calibrants. The calibration was carried out in such a manner that combined GPC-viscosity could be used to give ‘true’ molecular weight data and conventional GPC could also be applied. For the conventional GPC results, the system is calibrated with linear polyethylene or linear polypropylene. This correction has previously been shown to give good estimates of the true molecular weights for the linear polymers.

Synthesis of Unsymmetrical Pro-Ligands

[0204] Synthesis of Ethylene-Bridged [EB(.sup.tBu.sup.2Flu,I*)H.sub.2]

[0205] Having regard to Scheme 1 shown below, reaction of one equivalent of [(Ind.sup.#)H] with an excess of 1,2-dibromoethane afforded [(Ind*)CH.sub.2CH.sub.2Br] which was reacted with one equivalent of [(.sup.tBu.sup.2Flu)Li] to afford the new ethylene-bridged pro-ligand, [EB(.sup.tBu.sup.2Flu,I*)H.sub.2], as a colourless solid in good yield. FIG. 1 provides the .sup.1H NMR spectrum for EB(.sup.tBu.sup.2Flu,I*)H.sub.2].

##STR00020##

Synthesis of Silicon-Bridged [SB(.sup.tBu.sup.2Flu,I*)H.sub.2], [SB(Flu,I*)H.sub.2] and [SB(.sup.Me,PhInd,I*)H.sub.2]

[0206] Having regard to Scheme 2 shown below, various silicon-bridged unsymmetrical pro-ligands were accessed using the silane synthon, [.sup.R,R′Si(Ind*)Cl]. FIGS. 2, 3 and 4 show the .sup.1H NMR spectra for [.sup.Me.sup.2Si(Ind*)Cl], [.sup.iPr.sup.2Si(Ind*)Cl] and [.sup.Me,PrSi(Ind*)Cl] respectively.

##STR00021##

[0207] Having regard to Scheme 3 shown below, the synthesised silane synthon [.sup.Me.sup.2Si(Ind*)Cl] was separately reacted with one equivalent of [(.sup.tBu.sup.2Flu)Li], [(Flu)Li], and [(.sup.Me,PhInd)Li] to afford the new Si-bridged pro-ligands [SB(.sup.tBu.sup.2Flu,I*)H.sub.2], [SB(Flu,I*)H.sub.2] and [SB(.sup.Me,PhInd,I*)H.sub.2] respectively as colourless solids in very good yields. FIG. 5 shows the .sup.1H NMR spectrum for [SB(Flu,I*)H.sub.2]. FIG. 6 shows the X-ray crystallographic structure for [SB(.sup.tBu.sup.2Flu,I*)H.sub.2].

##STR00022##

Synthesis of Unsymmetrical Pro-Catalysts

[0208] Synthesis of [SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2] and [SB(.sup.tBu.sup.2Flu,I*)HfCl.sub.2]

[0209] Having regard to Scheme 4 shown below, stoichiometric reactions of [SB(.sup.tBu.sup.2Flu,I*)Li.sub.2] with MCl.sub.4 (M=Zr and Hf) were carried out in benzene at room temperature overnight to afford [SB(.sup.tBu.sup.2Flu,I*)MCl.sub.2] as bright orange solids in good yields. FIGS. 7 and 8 show the .sup.1H NMR spectra of [SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2] and [SB(.sup.tBu.sup.2Flu,I*)HfCl.sub.2] respectively. Single crystals of [SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2] and [SB(.sup.tBu.sup.2Flu,I*)HfCl.sub.2] suitable for X-ray crystallography were obtained by crystallisation in n-hexane solution at −30° C. FIGS. 9 and 10 show the X-ray crystallographic structures for [SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2] and [SB(.sup.tBu.sup.2Flu,I*)HfCl.sub.2] respectively

##STR00023##

Synthesis of .sup.Et2SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2 and .sup.Me,PropSB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2

[0210] Having regard to Scheme 5 outlined below, .sup.Et2SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2 and .sup.Me,PropSB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2 Si-bridged Zr pro-catalysts were prepared in 18% and 41% yields respectively.

##STR00024##

Synthesis of SB(.sup.tBu.sup.2Flu,I*.sup.,3-Ethyl)ZrCl.sub.2

[0211] Having regard to Scheme 6 outlined below, SB(.sup.tBu.sup.2Flu,I*,.sup.3-Ethyl)ZrCl.sub.2 Si-bridged Zr pro-catalyst was prepared.

##STR00025##

Synthesis of SB(Cp,I*)ZrCl.SUB.2

[0212] Having regard to Scheme 7 below, toluene (40 ml) was added to a LiCp (246 mg, 3.41 mmol) and Ind*SiMe2Cl (1 g, 3.41 mmol) in a Schlenk tube, dissolved in −5° C. THF (50 mL) and left to stir for two hours. .sup.nBuLi (4.7 mL, 1.6 M in hexanes, 7.51 mmol) was added, dropwise, over 30 minutes and the reaction left to stir for 12 hours. The solvent was removed in vacuo and the residue washed with pentane (3×40 mL) and dried to afford a grey powder. One equivalent of ZrCl.sub.4 (796 mg, 3.41 mmol) was added and the mixture dissolved in benzene and left to stir for sixty hours. The solution changed colour from green, to orange and finally red/brown. The solvent was removed under vacuum and the product extracted with pentane (3×40 mL) and filtered through Celite. The filtrate was concentrated in vacuo and stored at −34° C. This yielded SB(Cp,I*)ZrCl.sub.2 as an orange/brown precipitate in 23% yield (365 mg, 0.76 mmol). Orange crystals, suitable for single crystal X-ray diffraction, were grown from a concentrated solution in hexanes at −34° C.

[0213] .sup.1H NMR (d.sub.6-benzene): δ 6.59 (2H, dm, CpH), 5.60 (2H, dm, CpH), 2.52 (3H, s, ArMe), 2.48 (3H, s, ArMe), 2.26 (3H, s, ArMe), 2.15 (3H, s, ArMe), 2.05 (3H, s, ArMe), 1.97 (3H, s, ArMe), 0.72 (3H, s, SiMe), 0.64 (3H, s, SiMe).

[0214] .sup.13C{.sup.1H} NMR (d.sub.6-benzene): δ 135.65 (Ar), 135.13 (Ar), 134.86 (Ar), 131.11 (Ar), 131.50 (Ar), 131.15 (Ar), 129.16 (Ar), 126.35 (Ar), 125.92 (ArSi), 115.87 (CpH), 106.49 (CpH), 84.01 (CpSi), 21.69 (ArMe), 17.91 (ArMe), 17.64 (ArMe), 17.16 (ArMe), 16.92 (ArMe), 15.97 (ArMe), 5.59 (SiMe), 3.26 (SiMe).

[0215] MS (EI): Predicted: m/z 482.0372. Observed: m/z 482.0371. IR (KBr) (cm.sup.−1): 2961, 2925, 1543, 1260, 1029, 809, 668.

[0216] CHN Analysis (%): Expected: C, 54.74, H, 5.85. Found: C, 54.85, H, 5.94.

##STR00026##

Synthesis of SB(Cp,I*)HfCl.SUB.2

[0217] Having regard to Scheme 8 below, SB(Cp,I*)Li.sub.2 (1 g, 2.99 mmol) and HfCl.sub.4 (958 mg, 2.99 mmol) were added to a Schlenk tube. Benzene (100 mL) was added and the reaction was left to stir for 60 hours. The solution changed colour from brown to yellow. The solvent was the removed under vacuum and the product was extracted with pentane (3×40 mL) and filtered through Celite. The filtrate was concentrated in vacuo and stored at −34° C. yielding SB(Cp,I*)HfCl.sub.2 as yellow crystals, suitable for single crystal X-ray diffraction, in 24% yield (360 mg, 0.632 mmol).

[0218] .sup.1H NMR (d.sub.6-benzene): δ 6.54 (3H, dm, CpH), 5.53 (3H, dm, CpH), 2.57 (3H, s, ArMe), 2.56 (3H, s, ArMe), 2.25 (3H, s, ArMe), 2.20 (3H, s, ArMe), 2.09 (3H, s, ArMe), 2.03 (3H, s, ArMe), 0.65 (3H, s, SiMe), 0.57 (3H, s, SiMe).

[0219] .sup.13C{.sup.1H} NMR (d.sub.6-benzene): δ 134.55 (Ar), 134.18 (Ar), 133.51 (Ar), 131.73 (Ar), 131.05 (Ar), 129.64 (Ar), 126.23 (Ar), 125.18 (Ar), 124.38 (Ar), 113.33 (C.sub.pH), 107.32 (C.sub.pH), 82.33 (C.sub.pSi), 21.53 (ArMe), 17.68 (ArMe), 17.37 (ArMe), 16.77 (ArMe), 16.64 (ArMe), 15.51 (ArMe), 5.00 (SiMe), 3.00 (SiMe).

[0220] MS (EI): Predicted: m/z 570.0785. Observed: m/z 570.0701. IR (KBr) (cm.sup.−1): 2960, 2923, 1542, 1262, 1028, 812, 670.

[0221] CHN Analysis (%): Expected: C, 46.36, H, 4.95. Found: C, 46.52, H, 5.04.

##STR00027##

Synthesis of SB(Cp,I*)ZrCl(O-Me.sub.2-C.sub.6H.sub.3)

[0222] Having regard to Scheme 9 below, SB(Cp,I*)ZrCl.sub.2 (100 mg, 0.207 mmol) and 2,6-dimethyl potassium phenoxide (66 mg, 0.414 mmol) were added to a Schlenk tube, dissolved in benzene (20 mL), and left to stir for sixteen hours. The solvent was removed in vacuo and the product extracted with pentane (2×20 mL). The .sup.1H NMR spectra showed resonances corresponding to a mixture of two isomers. Thin, yellow crystals of isomer (a), suitable for single crystal X-ray diffraction were obtained when the solution was concentrated and stored in a −34° C. freezer. Purity was 94% by .sup.1H NMR spectroscopy and crystals were obtained in 15% yield (16 mg, 0.028 mmol).

[0223] Isomer (a):

[0224] .sup.1H NMR (d.sub.6-benzene): δ 7.06 (2H, dd, Ar.sub.phenH), 6.82 (1H, t, Ar.sub.phenH), 6.26 (1H, m, CpH), 6.13 (1H, m, CpH), 5.93 (1H, m, CpH), 5.61 (1H, m, CpH), 2.34 (3H, s, ArMe), 2.24 (3H, s, ArMe), 2.22 (6H, s, Ar.sub.phen Me), 2.19 (3H, s, ArMe), 2.18 (3H, s, ArMe), 2.15 (3H, s, ArMe), 1.99 (3H, s, ArMe), 0.81 (3H, s, SiMe), 0.75 (3H, s, SiMe).

[0225] Isomer (b):

[0226] .sup.1H NMR (d.sub.6-benzene): δ 6.88 (2H, dd, Ar.sub.phenH), 6.69 (1H, t, Ar.sub.phenH), 6.51 (1H, m, CpH), 6.02 (1H, m, CpH), 5.88 (1H, m, CpH), 5.80 (1H, m, CpH), 2.61 (3H, s, ArMe), 2.42 (6H, s, Ar.sub.phen Me), 2.40 (3H, s, ArMe), 2.08 (3H, s, ArMe), 1.99 (3H, s, ArMe), 1.64 (3H, s, ArMe), 1.48 (3H, s, ArMe), 0.64 (3H, s, SiMe), 0.61 (3H, s, SiMe).

##STR00028##

Synthesis of Supported Catalyst Systems

[0227] Synthesis of solid MAO/SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2] Catalyst System

[0228] Toluene (40 ml) was added to a Schlenk tube containing solid aluminoxane (solid MAO) (produced by TOSOH, Lot no. TY130408) (400 mg) and [SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2] (shown below) (13.6 mg) at room temperature. The slurry was heated to 60° C. and left, with occasional swirling, for one hour during which time the solution turned colourless and the solid colourised dark green. The resulting suspension was then left to cool down to room temperature and the toluene solvent was carefully filtered and removed in vacuo to obtain solid MAO/[SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2] catalyst as a grey, free-flowing powder in 85% yield (352 mg).

Synthesis of Solid MAO/rac-[(EBI*)ZrCl.SUB.2.], Catalyst System (Comparative Example)

[0229] Toluene (40 ml) was added to a Schlenk tube containing solid MAO (produced by TOSOH; Lot no. TY130408) (400 mg) and rac-[(EBI*)ZrCl.sub.2] (shown below) (8.6 mg) at room temperature. The slurry was heated to 60° C. and left, with occasional swirling, for one hour during which time the solution turned colourless and the solid colourised dark green. The resulting suspension was then left to cool down to room temperature and the toluene solvent was carefully filtered and removed in vacuo to obtain solid MAO/[SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2] catalyst as a grey, free-flowing powder in 85% yield (352 mg).

Synthesis of Solid MAO/meso-[(EBI*)ZrO.SUB.2.] Catalyst System (Comparative Example)

[0230] Toluene (40 ml) was added to a Schlenk tube containing solid MAO (produced by TOSOH; Lot no. TY130408) (400 mg) and meso-[(EBI*)ZrCl.sub.2] (shown below) (8.6 mg) at room temperature. The slurry was heated to 60° C. and left, with occasional swirling, for one hour during which time the solution turned colourless and the solid colourised dark green. The resulting suspension was then left to cool down to room temperature and the toluene solvent was carefully filtered and removed in vacuo to obtain solid MAO/[SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2] catalyst as a grey, free-flowing powder in 85% yield (352 mg).

Synthesis of Solid MAO/rac-[(SBI*)ZrCl.SUB.2.] Catalyst System (Comparative Example)

[0231] Toluene (40 ml) was added to a Schlenk tube containing solid MAO (produced by TOSOH; Lot no. TY130408) (400 mg) and rac-[(SBI*)ZrCl.sub.2] (shown below) (9.1 mg) at room temperature. The slurry was heated to 60° C. and left, with occasional swirling, for one hour during which time the solution turned colourless and the solid colourised dark green. The resulting suspension was then left to cool down to room temperature and the toluene solvent was carefully filtered and removed in vacuo to obtain solid MAO/[SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2] catalyst as a grey, free-flowing powder in 85% yield (352 mg).

##STR00029##

Ethylene Polymerisation Studies

Homopolymerisation of Ethylene

[0232] Solid MAO/[Zr-Complex] catalysts (Zr-Complex=rac-[(EBI*)ZrCl.sub.2], meso-[(EBI*)ZrCl.sub.2], rac-[(SBI*)ZrCl.sub.2], [SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2]) were tested for their ethylene homopolymerisation activity under slurry conditions in the presence of tri(isobutyl)aluminium (TIBA), an aluminium-based scavenger. The reactions were performed under 2 bar of ethylene in a 200 mL ampoule, with 10 mg of the catalyst suspended in 50 mL of hexane. The reactions were run for 60 minutes controlled by heating in an oil bath. The resulting polyethylene was immediately filtered under vacuum through a dry sintered glass frit. The polyethylene product was then washed with pentane (2×25 ml) and then dried on the frit for at least one hour. The tests were carried out at least twice for each individual set of polymerisation conditions.

[0233] FIG. 11 shows the polymerisation productivity (Kg(PE)g(Cat).sup.−1h.sup.−1) vs time (sec) for the polymerisation of ethylene using Solid MAO based catalysts at 70° C. FIG. 12 shows the polymerisation productivity (Kg(PE)g(Cat).sup.−1h.sup.−1) vs time (sec) for the polymerisation of ethylene using Solid MAO based catalysts at 80° C. The data demonstrate markedly superior activity for the solid MAO/[SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2] catalyst system of the invention, when compared with comparative examples solid MAO/rac-[(EBI*)ZrCl.sub.2], solid MAO/meso-[(EBI*)ZrCl.sub.2] and solid MAO/rac-[(SBI*)ZrCl.sub.2].

[0234] Table 1 below shows GPC results for the homopolymerisation of ethylene using Solid MAO/[complex] (complex=rac-[(EBI*)ZrCl.sub.2], meso-[(EBI*)ZrCl.sub.2], rac-[(SBI*)ZrCl.sub.2], [SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2]).

TABLE-US-00001 TABLE 1 GPC results for the homopolymerisation of ethylene using Solid MAO/[complex]. Polymerisation conditions: 5 mL heptane, P.sub.ethylene = 120 psi, and n.sub.(TEA) = 10 μmol. T = 80° C. T = 70° C. M.sub.w M.sub.w/ Catalyst M.sub.w (kDa) M.sub.w/M.sub.n (kDa) M.sub.n Solid MAO/rac-[(EBI*)ZrCl.sub.2] 199 2.3 194 2.7 Solid MAO/meso-[(EBI*)ZrCl.sub.2] 242 2.7 210 2.7 Solid MAO/rac-[(SBI*)ZrCl.sub.2] 273 3.1 367 3.3 Solid MAO/[SB(.sup.tBu.sub.2Flu,I*)ZrCl.sub.2]  722† 3.5  626† 3.6 †Values underestimated due to incomplete sample elution. Note: maximum error is 10% on M.sub.w.

[0235] Having regard to the data presented in Table 1, unsymmetrical complex [SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2] is seen to afford polyethylene having a significantly higher molecular weight than that afforded by the comparator catalyst systems. Moreover, the increase in molecular weight is not accompanied by an increase in polydispersity. High molecular weight materials with low polydispersity are highly favoured by industry in special applications.

Copolymerisation of Ethylene and 1-Hexene

[0236] Solid MAO/[Zr-Complex] catalysts (Zr-Complex=rac-[(EBI*)ZrCl.sub.2], meso-[(EBI*)ZrCl.sub.2], rac-[(SBI*)ZrCl.sub.2], [SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2]) were tested for their ethylene/1-hexene copolymerisation activity under slurry conditions in the presence of tri(isobutyl)aluminium (TIBA), an aluminium-based scavenger. The reactions were performed under 2 bar of ethylene in a 200 mL ampoule, with 10 mg of the catalyst suspended in 50 mL of hexane. The reactions were run for 60 minutes controlled by heating in an oil bath. The resulting polyethylene was immediately filtered under vacuum through a dry sintered glass frit. The polyethylene product was then washed with pentane (2×25 ml) and then dried on the frit for at least one hour. The tests were carried out at least twice for each individual set of polymerisation conditions.

[0237] FIG. 13 shows activity vs. time for the copolymerisation of ethylene and 1-hexene using Solid MAO based catalyst. FIG. 14 shows activity vs time for the copolymerisation of ethylene and 1-hexene using Solid MAO based catalyst with variation of the 1-hexene feed, when P.sub.ethylene=120 PSI. FIG. 15 shows activity vs time for the copolymerisation of ethylene and 1-hexene using Solid MAO based catalyst with variation of the 1-hexene feed, when P.sub.ethylene=80 PSI. The data demonstrate superior copolymerisation activity for the solid MAO/[SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2] catalyst system of the invention, when compared with comparative examples solid MAO/rac-[(EBI*)ZrCl.sub.2], solid MAO/meso-[(EBI*)ZrO.sub.2] and solid MAO/rac-[(SBI*)ZrCl.sub.2].

[0238] Table 2 below summarises activity results for the copolymerisation of ethylene and 1-hexene using Solid MAO/[complex].

TABLE-US-00002 TABLE 2 Activity results for the copolymerisation of ethylene and 1-hexene using Solid MAO/[complex]. Polymerisation conditions: 5 mL heptane, T = 70° C., P.sub.ethylene = 120 psi, and n.sub.(TEA) = 15 μmol. [Hexene].sub.feed 0 vol % 2 vol % 5 vol % Activity Activity Activity kg(cop) kg(cop) kg(cop) Catalyst g(cat).sup.−1 h.sup.−1 g(cat).sup.−1 h.sup.−1 g(cat).sup.−1 h.sup.−1 Solid MAO/ 6.8 7.7 8.9 rac-[(EBI*)ZrCl.sub.2] Solid MAO/ 0.3 0.3 0.3 meso-[(EBI*)ZrCl.sub.2] Solid MAO/ 6.1 7.4 6.6 rac-[(SBI*)ZrCl.sub.2] Solid MAO/ 9.8 16.4 18.2 [SB(.sup.tBu.sub.2Flu,I*)ZrCl.sub.2]

[0239] The results presented in Table 2 demonstrate that the Solid MAO/[SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2] catalytic complex of the invention exhibits markedly superior activity across a range of hexane concentrations, when compared with comparator catalytic complexes.

[0240] Tables 3 and 4 below shows GPC results for the copolymerisation of ethylene and 1-hexene using Solid MAO/[complex] (complex=rac-[(EBI*)ZrCl.sub.2], meso-[(EBI*)ZrCl.sub.2], rac-[(SBI*)ZrCl.sub.2], [SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2]).

TABLE-US-00003 TABLE 3 GPC results for the copolymerisation of ethylene and 1-hexene using Solid MAO/[complex]. Polymerisation conditions: 5 mL heptane, T = 70° C., P.sub.ethylene = 120 psi, and n.sub.(TEA) = 15 μmol. [Hexene].sub.feed = 5 vol % [Hexene] = 10 vol % Catalyst M.sub.w (kDa) M.sub.w/M.sub.n M.sub.w (kDa) M.sub.w/M.sub.n Solid MAO/ 227 2.5 228 2.6 rac-[(EBI*)ZrCl.sub.2] Solid MAO/ 271 3.3 224 2.8 meso-[(EBI*)ZrCl.sub.2] Solid MAO/ 302 3.3 244 2.8 rac-[(SBI*)ZrCl.sub.2] Solid MAO/  270† 2.1 479 3.1 [SB(.sup.tBu.sub.2Flu,I*)ZrCl.sub.2] †Values underestimated due to incomplete sample elution. Note: maximum error is 10% on M.sub.w.

TABLE-US-00004 TABLE 4 GPC results for the copolymerisation of ethylene and 1-hexene using Solid MAO/[complex]. Polymerisation conditions: 5 mL heptane, T = 70° C., P.sub.ethylene = 80 psi, and n.sub.(TEA) = 15 μmol [Hexene].sub.feed = 2 vol % [Hexene] = 5 vol % Catalyst M.sub.w (kDa) M.sub.w/M.sub.n M.sub.w (kDa) M.sub.w/M.sub.n Solid MAO/ 207 2.3 231 2.6 rac-[(EBI*)ZrCl.sub.2] Solid MAO/ 213 2.7 212 2.8 meso-[(EBI*)ZrCl.sub.2] Solid MAO/ 378 4.2 311 3.5 rac-[(SBI*)ZrCl.sub.2] Solid MAO/  310* 3.0  235* 1.3 [SB(.sup.tBu.sub.2Flu,I*)ZrCl.sub.2]

[0241] Table 5 below illustrates the incorporation of 1-hexene in the copolymerisation of ethylene and 1-hexene by .sup.13C{.sup.1H} NMR spectroscopy and crystallization elution fractionation analysis.

TABLE-US-00005 TABLE 5 .sup.13C{.sup.1H} NMR spectroscopy and CEF results of the incorporation of 1-hexene in the copolymerisation of ethylene and 1-hexene using Solid MAO/[complex]. Polymerisation conditions: 5 mL heptane, T = 70° C., P.sub.ethylene = 120 psi, and n.sub.(TEA) = 15 μmol. [Hexene].sub.feed [Hexene].sub.cop T.sub.el,max IV Catalyst (% v/v) (mol %) (° C.) (dL/g) Solid MAO/ 5 0.2 110.7 1.9 rac-[(EBI*)ZrCl.sub.2] 10 0.4 109.9 2.0 Solid MAO/ 5 0.2 110.4 2.0 meso-[(EBI*)ZrCl.sub.2] 10 0.5 109.6 1.8 Solid MAO/ 5 0.4 108.4 1.7 rac-[(SBI*)ZrCl.sub.2] 10 0.8 108.8 1.9 Solid MAO/ 5 2.0 — — [SB(.sup.tBu.sub.2Flu,I*)ZrCl.sub.2] 10 3.8 96.6 3.6

[0242] The results outlined in Tables 3-5 point to a well-behaved copolymerization process with narrow inter-molecular co-monomer distribution, as analysed by GPC and CEF.

Further Polymerisation Studies

[0243] Table 6 below presents the activity results (kg.sub.PE/g.sub.CAT/h) for the polymerisation of ethylene in slurry using SB(Cp,I*)ZrCl.sub.2 supported on Solid MAO. The activity of this complex is compared with that of (.sup.nBuCp).sub.2ZrCl.sub.2 and (Ind).sub.2ZrCl.sub.2, when supported on solid MAO, which are not encompassed by the invention.

TABLE-US-00006 TABLE 6 Activity results (kg.sub.PE/g.sub.CAT/h) for the polymerisation of ethylene in slurry, complex supported on Solid MAO T P Time V Activity Complex (° C.) (bar) (minutes) (mL) kg.sub.PE/g.sub.CAT/h SB(Cp,I*)ZrCl.sub.2 80 8 70 1000 3.2 (.sup.nBuCp).sub.2ZrCl.sub.2 80 8 70 1000 1.2 (Ind).sub.2ZrCl.sub.2 80 8 70 1000 1.6

[0244] Table 7 below presents the activity results (kg.sub.PE/g.sub.CAT/h) and molecular weight (g/mol) for the polymerisation of ethylene in slurry using supported on Solid MAO/SB(Cp,I*)ZrCl.sub.2 as a function of H.sub.2 feeding content.

TABLE-US-00007 TABLE 7 Activity results (kg.sub.PE/g.sub.CAT/h) and molecular weight (g/mol) for the polymerisation of ethylene in slurry using supported on Solid MAO/SB(Cp,I*)ZrCl.sub.2 as a function of H.sub.2 feeding content. H.sub.2 T P Time V Activity M.sub.w (%) (° C.) (bar) (minutes) (mL) kg.sub.PE/g.sub.CAT/h (g/mol) 0 80 8 5 14.2 350000 0.8 80 8 5 9.7 29000 1.6 80 8 5 5.7 22000 0 80 8 60 1000 14.2 289345 2 80 8 60 1000 4.8 12434 3.5 80 8 60 1000 3.2 10895

[0245] Table 8 below presents the activity results (kg.sub.PE/g.sub.CAT/h/bar), molecular weight (g/mol) and CEF value for the polymerisation of ethylene and co-polymerisation of ethylene and 1-hexene in slurry using various compositions of the invention (supported on Solid MAO).

TABLE-US-00008 TABLE 8 Activity results (kg.sub.PE/g.sub.CAT/h/bar), molecular weight (g/mol) and CEF value for the polymerisation of ethylene and co-polymerisation of ethylene and 1-hexene in slurry using complexes supported on Solid MAO. [Hexene].sub.feed [Hexene].sub.cop Activity M.sub.w M.sub.w/ T.sub.el, max Complex (μL) (mol %) kg.sub.PE/g.sub.CAT/h (kg/mol) M.sub.n (° C.) .sup.Et2SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2 0 0 8.1 279000 2.9 111.5 .sup.Et2SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2 125 1.3 29.2 242000 2.8 103.5 .sup.Et2SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2 250 2.8 6.1 232000 2.1 99.1 SB(Cp,I*)ZrCl.sub.2 0 0 14.2 73000 2.6 111.1 SB(Cp,I*)ZrCl.sub.2 125 0.6 20.2 85000 2.4 107.2 SB(Cp,I*)ZrCl.sub.2 250 1.0 18.5 60000 2.1 104.1 .sup.Me, PropSB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2 0 0 1.0 169000 3.2 111.6 .sup.Me, PropSB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2 250 3.2 8.4 268000 2.4 98.4 SB(.sup.tBu.sup.2Flu,I*.sup., 3-Ethyl)ZrCl.sub.2 0 0 1.5 171000 5.3 111.6 SB(.sup.tBu.sup.2Flu,I*.sup., 3-Ethyl)ZrCl.sub.2 250 3.6 9.1 212000 2.3 95.1 SB(Cp,I*)HfCl.sub.2 0 0 0.5 168000 2.3 111.8 SB(.sup.tBu.sup.2Flu,I*)HfCl.sub.2 0 0 1.1 318000 2.4 111.9 Polymerisation conditions: 80° C., 8 bar, 5 mL Heptane

[0246] FIGS. 28 and 29 demonstrate that the solid MAO supported SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2 and solid MAO supported SB(Cp,I*)ZrCl.sub.2 catalysts possess the highest activities. Changing the bridge to di-ethyl and methyl-propyl led to similar activities.

[0247] FIG. 30 shows that solid MAO supported SB(.sup.tBu.sup.2Flu,I*)HfCl.sub.2 is 3 times faster than solid MAO supported SB(Cp,I*)HfCl.sub.2 but 25% slower than its zirconium analogue (FIG. 26).

[0248] FIG. 31 shows that good polyethylene morphology were obtained when solid MAO supported/.sup.Et2SB(.sup.tBu.sup.2Flu,I*)ZrCl.sub.2 and solid MAO supported/SB(Cp,I*)ZrCl.sub.2 were used as catalysts, which demonstrates monodisperse PE.

[0249] FIG. 32 shows that in similar conditions solid MAO supported/SB(Cp,I*)ZrCl.sub.2 is better controlled and affords a higher activity (3.2 kg.sub.PE/g.sub.CAT/h/bar) than known industrial catalysts (solid MAO supported (.sup.nBuCp).sub.2ZrCl.sub.2 and solid supported (Ind).sub.2ZrCl.sub.2 with activities of 1.2 and 1.6 kg.sub.PE/g.sub.CAT/h/bar respectively). This demonstrates the huge potential for solid MAO supported/SB(Cp,I*)ZrCl.sub.2 to be used as catalyst for the formation of PE wax.

[0250] FIGS. 33 and 34 show the decrease in activity and in molecular weight with increasing H.sub.2 content when used as co-feed.

[0251] FIG. 35 shows that most of the catalysts afforded a higher activity for the copolymerisation of ethylene and 1-hexene than the just for the homopolymerisation of ethylene.

Synthesis of Solid MAO

[0252] Various samples of solid MAO were prepared according to the below synthetic protocol:

##STR00030##

[0253] The effect of varying Al:O ratio on the BET surface area and ethylene polymerisation activity was investigated. The results are presented in Table 9 below:

TABLE-US-00009 TABLE 9 Effect of varying Al:O ratio on the BET surface area and ethylene polymerisation activity of Me.sub.2SB(.sup.tBu2Flu, I*)ZrCl.sub.2 supported on solid MAO TMA Content/ BET/ Activity/ Al:O mol % % yield m.sup.2mmol.sub.Al.sup.−1 Supported? kg.sub.PEmol.sub.zr.sup.−1h.sup.−1 1.0 1.0 26 11.9 No — 1.1 20.8 93 16.3 Yes 4777 1.2 15.1 82 15.3 Yes 2613 1.3 7.5 53 10.4 Yes 5518 1.4 11.0 42 9.9 Yes 2730 1.6 11.6 58 8.4 Yes — TMA amount kept constant. Benzoic acid content varied.

[0254] While specific embodiments of the invention have been described herein for the purpose of reference and illustration, various modifications will be apparent to a person skilled in the art without departing from the scope of the invention as defined by the appended claims.

REFERENCES

[0255] 1 J. Cosier, A. M. Glazer, J. Appl. Cryst. 19 (1986) 105 [0256] 2 Z. Otwinowski, W. Minor, Methods Enzymol. 276 (1997) 307 [0257] 3 L. Palatinus, G. Chapuis, J. Appl. Cryst. 40 (2007) 786 [0258] 4 P. W. Betteridge, J. R. Carruthers, R. I. Cooper, K. Prout, D. J. Watkin, J. Appl. Cryst. 36 (2003) 1487 [0259] 5 R. I. Cooper, A. L. Thompson, D. J. Watkin, J. Appl. Cryst. 43 (2010) 1100