Process for manufacturing ultra high molecular weight polymers using novel bridged metallocene catalysts

1. A process of manufacturing ultra high molecular weight ethylene polymers comprising predominantly polyethylene, wherein the process comprises reacting ethylene in the presence of a catalyst system which includes a compound of Formula I to produce a polymer having a viscosimetrically determined molecular weight of greater than 1×10 6 g/mol

whereby:

M 1 is a transition metal of the 4 th to 6 th group of the periodic table, wherein the oxidation level of said transition metal does not equal zero;

R 1 is equal to hydrogen or a C 1 -C 20 -carbonaceous group or a halogen atom;

R 2 is equal to hydrogen or a C 1 -C 20 carbonaceous group or a halogen atom;

R 3 , R 10 are each identical or different and are a C 1 -C 20 carbonaceous group, provided that at least one radical R 3 or R 10 is a C 2 -C 20 carbonaceous group;

R 4 , R 5 , R 6 , R 7 , R 8 , R 11 , R 12 , R 13 , R 14 , R 15 are each identical or different and are a hydrogen or a halogen atom or a C 1 -C 20 carbonaceous group, whereby, optionally, two or several consecutively form a cyclic system; and

R 9 is a bridge between the ligands, which is represented by the following formulas:

whereby:

M 2 is either silicon, germanium or tin; and

R 16 , R 17 are each identical or different and are each hydrogen or a C 1 -C 20 carbonaceous group or a halogen atom.

2. The process according to claim 1 , wherein M 1 is selected from the group consisting of Ti, Zr, Hf, V, Mo, Cr and Nb.

3. The process according to claim 1 , wherein at least one of R 4 , R 5 , R 6 , R 7 , R 8 , R 11 , R 12 , R 13 , R 14 , and R 15 includes a cyclic group.

4. The process according to claim 1 , wherein for the compound of Formula I:

M 1 is a transition metal of the 4 th group of the periodic table, wherein the oxidation level of said transition metal does not equal zero;

R 1 is hydrogen or a C 1 -C 20 -carbonaceous group or a halogen atom;

R 2 is hydrogen or a C 1 -C 20 carbonaceous group or a halogen atom;

R 3 is a C 2 -C 20 carbonaceous group;

R 10 is a C 1 -C 10 carbonaceous group;

R 4 , R 6 , R 7 , R 8 , R 11 , R 13 , R 14 , R 15 are each hydrogen;

R 5 , R 12 are each identical or different and are a C 1 -C 20 carbonaceous group, of which at least one includes a cyclic group; and

R 9 is a bridge between the ligands, which is represented by the following formulas:

whereby:

M 2 is silicon; and

R 16 , R 17 are each identical or different and equal to hydrogen or a C 1 -C 20 carbonaceous group or a halogen atom.

5. The process according to claim 4 , wherein R 5 , R 12 are identical or different and are selected from the group consisting of C 6 -C 20 aryl, C 6 -C 20 fluoroaryl, C 6 -C 20 aryloxy, C 7 -C 20 arylalkyl, C 7 -C 20 alkylaryl, C 7 -C 20 aryloxyaryl, C 4 -C 20 heterocycloalkyl, C 8 -C 20 arylalkenyl, and C 8 -C 20 arylalkinyl.

6. The process according to claim 4 , wherein both of R 5 and R 12 include a cyclic group.

7. The process according to claim 4 , wherein R 3 is an α- or β-position branched carbonaceous group or a carbonaceous group cyclized in a α- or β-position.

8. The process according to claim 1 , wherein for the compound of Formula I:

M 1 is zirconium; and

R 1 , R 2 are identical and are each chlorine, methyl or phenolate; and

R 3 is an isopropyl-, isobutyl-, cyclopentyl-, cyclohexyl-, tert-butyl-, or a phenyl group; and

R 10 is a C 1 -C 10 carbonaceous group and is an alkyl group; and

R 4 , R 6 , R 7 , R 8 , R 11 , R 13 , R 14 , R 15 are each hydrogen; and

R 5 , R 12 are identical or different and are a C 1 -C 20 carbonaceous group, where at least one includes a phenyl group which supports a C 1 -C 4 -alkyl group; and

R 9 is a bridge between the ligands, which is represented by the following formulas:

whereby:

M 2 is silicon; and

R 16 , R 17 are each identical or different and are hydrogen or a C 1 -C 20 carbonaceous group or a halogen atom.

9. The process according to claim 8 , wherein R 5 , R 12 are identical and include a phenyl group which supports a C 1 -C 4 -alkyl group in the para position.

10. The process according to claim 1 , wherein the compound of Formula I has a structure corresponding to one or more of the following:

11. The process according to claim 1 , wherein the compound of Formula I has a structure corresponding to the following formula:

12. The process according to claim 1 , wherein the compound of Formula I has a structure corresponding to the following formula:

13. The process according to claim 1 , wherein the compound of Formula I has a structure corresponding to the following formula:

14. The process according to claim 1 , wherein the compound of Formula I has a structure corresponding to the following formula:

15. The process according to claim 1 , wherein the compound in Formula I is present in a supported form.

16. The process according to claim 1 , whereby the ethylene used in the process contains additional olefins with 3-20 carbon atoms.

17. The process according to claim 16 , whereby the ethylene used in the process contains additional olefins with 3-10 carbon atoms.

18. The process according to claim 16 , wherein the additional olefins are selected from the group consisting of propene, butene, 1-pentene, 1-hexene, 1-decene, 4-methyl-1-pentene, 1-octene, styrene, 1,3-butadiene, 1,4-hexadiene, vinyl norbornene, norbornadiene, ethyl norbornadiene, norbornene, cyclopentadiene, tetracyclododecene, methylnorbornene, and combinations thereof.

19. The process according to claim 1 , wherein the ethylene is copolymerized with an alpha olefin having 3 to 8 carbon atoms.

20. The process according to claim 19 , wherein the alpha olefin is selected from the group consisting propene, butene, 1-pentene, 1-hexene, styrene, butadiene, and combinations thereof.

21. The process according to claim 1 , wherein the ethylene is homopolymerized.

22. The process according to claim 1 , wherein the ethylene is co-polymerized with propene.

23. The process according to claim 1 , wherein the process produces a polymer having a molecular weight distribution M w /M n of from 2 to 6.

24. A method of using a catalyst system to produce ultra-high molecular weight ethylene homopolymer or copolymers, wherein the method comprises reacting ethylene in the presence of said catalyst system to produce a polymer comprising predominantly polyethylene having a viscosimetrically determined molecular weight of greater than 1×10 6 q/mol, wherein said catalyst system contains:

(i) at least one catalyst having the formula:

whereby:

M 1 is a transition metal of the 4 th to 6 th group of the periodic table, wherein the oxidation level of said transition metal does not equal zero;

R 1 is equal to hydrogen or a C 1 -C 20 -carbonaceous group or a halogen atom;

R 2 is equal to hydrogen or a C 1 -C 20 carbonaceous group or a halogen atom;

R 3 , R 10 are each identical or different and are a C 1 -C 20 carbonaceous group, provided that at least one radical R 3 or R 10 is a C 2 -C 20 carbonaceous group;

R 4 , R 5 , R 6 , R 7 , R 8 , R 11 , R 12 , R 13 , R 14 , R 15 are each identical or different and are a hydrogen or a halogen atom or a C 1 -C 20 carbonaceous group, whereby, optionally, two or several consecutively form a cyclic system; and

R 9 is a bridge between the ligands, which is represented by the following formulas:

whereby:

M 2 is either silicon, germanium or tin; and

R 16 , R 17 are each identical or different and are each hydrogen or a C 1 -C 20 carbonaceous group or a halogen atom; and

(ii) at least one co-catalyst.

25. The process according to claim 24 , wherein the co-catalyst is a Lewis acid.

26. The process according to claim 24 , wherein the co-catalyst is an aluminoxane compound.

27. The process according to claim 24 , wherein the co-catalyst is a methylaluminoxane compound.

28. A process of manufacturing ultra high molecular weight ethylene polymers comprising predominantly polyethylene, wherein the process comprises reacting ethylene in the presence of a catalyst system to produce a polymer having a viscosimetrically determined molecular weight of greater than 1×10 6 g/mol, wherein the catalyst system comprises a bridged metallocene catalyst compound having a zirconium dichloride central functionality and a dimethyl silandiyl bridge between five-membered rings of the metallocene compound, and wherein the rings are indenyl, with the proviso that both rings are substituted at the 2-position with respect to the dimethyl silanediyl bridge with a C 1 -C 20 carbonaceous group and at least one of the rings is substituted with a C 2 -C 20 carbonaceous group at the 2 position with respect to the dimethyl silandiyl bridge.