Metallic complex catalyst, polymerization methods employing same and polymer products thereof

Patent metadata

Field	Value
Publication number	US-10457765-B2
Application number	US-201515315011-A
Country	US
Kind code	B2
Filing date	May 26, 2015
Priority date	May 31, 2014
Publication date	Oct 29, 2019
Grant date	Oct 29, 2019

Abstract

Metallic complexes having indenyl ligands can be used as an ingredient of a catalyst system. The catalyst system can be used in polymerizations of ethylenically unsaturated hydrocarbon monomers that include both olefins and polyenes. Embodiments of the catalyst system can provide interpolymers that include polyene mer and from 40 to 75 mole percent ethylene mer, with a plurality of the ethylene mer being randomly distributed. The catalyst system also can be used in solution polymerizations conducted in C 5 -C 12 alkanes, yielding interpolymers that include at least 10 mole percent ethylene mer.

First claim

That which is claimed is:

1. A catalyst composition useful for polymerizing mixtures of polyene and α-olefin mer, said composition comprising a complex defined by the general formula

where
M represents a Group 3 metal atom;
L represents a neutral Lewis base;
z is an integer of from 0 to 3 inclusive;
m is 1 or 2 with the proviso that, when m is 2, the silyl groups are at the 1 and 3 positions of the indenyl ligand;
n is 1 or 2;
each R 1 independently is a C 1 -C 20 alkyl group or a —(CH 2 )R 3 group with R 3 being a phenyl group optionally substituted with an alkyl group, with the proviso that at least one R 1 is —(CH 2 )R 3 ; and
R 2 is an X-type, monoanionic ligand,

wherein, when z is not zero, one L group and one R 2 group can join so as to provide, together with the M atom to which each is bonded, a cyclic moiety.

2. The catalyst composition of claim 1 wherein z of said complex is 0.

3. The catalyst composition of claim 1 wherein M of said complex is a lanthanide metal atom.

4. The catalyst composition of claim 1 wherein m of said complex is 1, said silyl group being bonded at the 1-position of the indenyl ligand.

5. A process for providing a polymer, said process comprising contacting one or more ethylenically unsaturated hydrocarbons with the catalyst composition of claim 1 and allowing said polymer to form therefrom, said process optionally further comprising reacting said polymer with a functionalizing agent so as to provide terminal functionality to said polymer.

6. The process of claim 5 wherein said one or more ethylenically unsaturated hydrocarbons comprises at least one conjugated diene compound.

7. The process of claim 6 wherein said one or more ethylenically unsaturated hydrocarbons further comprises at least one α-olefin.

8. The process of claim 7 wherein at least 50 mole percent of the conjugated diene mer are incorporated in 1,4-cis configuration.

9. The process of claim 8 wherein said polymer comprises at least one block of conjugated diene mer and at least one block of randomly distributed conjugated diene and α-olefin mer.

10. The catalyst composition of claim 1 wherein each R 1 independently is a —(CH 2 )R 3 group with R 3 being a phenyl group optionally substituted with an alkyl group.

11. A catalyst composition useful for polymerizing mixtures of polyene and α-olefin mer, said composition comprising a complex defined by the general formula

where
M represents a Group 3 metal atom;
L represents a neutral Lewis base;
z is an integer of from 0 to 3 inclusive;
m is 1 or 2 with the proviso that, when m is 2, the silyl groups are at the 1 and 3 positions of the indenyl ligand;
n is 2;
each R 1 independently is a C 1 -C 20 alkyl group or a —(CH 2 )R 3 group with R 3 being a phenyl group optionally substituted with an alkyl group, with the proviso that at least one R 1 is —(CH 2 )R 3 ; and
R 2 is an X-type, monoanionic ligand,

wherein, when z is not zero, one L group and one R 2 group can join so as to provide, together with the M atom to which each is bonded, a cyclic moiety.

12. The catalyst composition of claim 11 wherein z of said complex is 0.

13. The catalyst composition of claim 11 wherein M of said complex is a lanthanide metal atom.

14. The catalyst composition of claim 11 wherein each R 1 independently is a —(CH 2 )R 3 group with R 3 being a phenyl group optionally substituted with an alkyl group.

15. The catalyst composition of claim 11 wherein m of said complex is 1, said silyl group being bonded at the 1-position of the indenyl ligand.

16. A catalyst composition useful for polymerizing mixtures of polyene and α-olefin mer, said composition comprising a complex defined by the general formula

where
M represents a lanthanide metal atom;
L represents a neutral Lewis base;
z is an integer of from 0 to 3 inclusive;
m is 1, in which case the silyl group is bonded at the 1-position of the indenyl ligand, or 2, in which case the silyl groups are at the 1 and 3 positions of the indenyl ligand;
n is 2;
each R 1 independently is a C 1 -C 20 alkyl group or a —(CH 2 )R 3 group with R 3 being a phenyl group optionally substituted with an alkyl group, with the proviso that at least one R 1 is —(CH 2 )R 3 ; and
R 2 is an X-type, monoanionic ligand,

wherein, when z is not zero, one L group and one R 2 group can join so as to provide, together with the M atom to which each is bonded, a cyclic moiety.

17. The catalyst composition of claim 16 wherein z of said complex is 0.

18. The catalyst composition of claim 16 wherein each R 1 independently is a —(CH 2 )R 3 group with R 3 being a phenyl group optionally substituted with an alkyl group.

Assignees

• Bridgestone Corp

Inventors

• Qin Zengquan
• Abell Joshua P

Classifications

• C07F7/10 Primary

  containing nitrogen {having a Si-N linkage} · CPC title

• C08F236/06 Primary

  Butadiene · CPC title

• C08F2420/03

  Cp or analog not bridged to a non-Cp X ancillary neutral donor · CPC title

• C08F4/545

  rare earths being present, e.g. triethylaluminium + neodymium octanoate · CPC title

• C08F2800/10

  as molar percentages · CPC title