Polymerization catalyst having a tetradentate ligand
A new olefin polymerization catalyst is ligated with a tetradentate ligand having a phenoxy/amino/ether/phenoxy (O/N/O/O) atom donor set. The new polymerization catalyst which is based on zirconium or hafnium produces an ethylene copolymer with high molecular weight and high comonomer incorporation levels.
1 . A polymerization process comprising polymerizing ethylene with one or more C 3-12 alpha olefins in the presence of a polymerization catalyst system comprising:
i) an olefin pre-polymerization catalyst having the formula:
wherein M is Hf or Zr;
R 1 is a hydrogen, an optionally substituted hydrocarbyl group, or an optionally substituted heteroatom containing hydrocarbyl group;
each R 2 is independently an optionally substituted hydrocarbyl group, or an optionally substituted heteroatom containing hydrocarbyl group;
each of A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 , A 10 , A 11 and A 12 is a hydrogen, a halide, an optionally substituted hydrocarbyl group, or an optionally substituted heteroatom containing hydrocarbyl group;
L is an optionally substituted bivalent hydrocarbyl group, or an optionally substituted bivalent heteroatom containing hydrocarbyl group;
optionally two or more adjacent A groups may be part of a ring structure; and each X is independently an activatable leaving group; and
ii) a catalyst activator.
2 . The polymerization process of claim 1 wherein each R2 has the formula:
3 . The polymerization process of claim 2 wherein L is a bivalent hydrocarbyl group.
4 . The polymerization process of claim 3 wherein L is a bivalent n-propyl group having the formula: —CH 2 CH 2 CH 2 —.
5 . The polymerization process of claim 4 wherein A 2 and A 8 are each a methyl group.
6 . The polymerization process of claim 5 wherein A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 , A 10 , A 11 and A 12 are each a hydrogen.
7 . The polymerization process of claim 6 wherein R 1 is a methyl group.
8 . The polymerization process of claim 1 wherein the polymerization process is a solution phase polymerization process carried out in a solvent.
9 . The polymerization process of claim 8 wherein the polymerization process comprises polymerizing ethylene with 1-octene.
10 . An olefin pre-polymerization catalyst having the formula:
wherein M is Hf or Zr;
R 1 is a hydrogen, an optionally substituted hydrocarbyl group, or an optionally substituted heteroatom containing hydrocarbyl group;
each R 2 is independently an optionally substituted hydrocarbyl group, or an optionally substituted heteroatom containing hydrocarbyl group;
each of A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 , A 10 , A 11 and A 12 is a hydrogen, a halide, an optionally substituted hydrocarbyl group, or an optionally substituted heteroatom containing hydrocarbyl group;
L is an optionally substituted bivalent hydrocarbyl group, or an optionally substituted bivalent heteroatom containing hydrocarbyl group;
optionally two or more adjacent A groups may be part of a ring structure; and each X is independently an activatable leaving group.
11 . The pre-polymerization catalyst of claim 10 wherein each R 2 has the formula:
12 . The pre-polymerization catalyst of claim 11 wherein L is a bivalent hydrocarbyl group.
13 . The pre-polymerization catalyst of claim 12 wherein L is a bivalent n-propyl group having the formula: —CH 2 CH 2 CH 2 —.
14 . The pre-polymerization catalyst of claim 13 wherein A 2 and A 8 are each a methyl group.
15 . The pre-polymerization catalyst of claim 14 wherein A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 , A 10 , A 11 and A 12 are each a hydrogen.
16 . The pre-polymerization catalyst of claim 15 wherein R 1 is a methyl group.
17 . An olefin polymerization catalyst system comprising:
i) an olefin pre-polymerization catalyst having the formula:
wherein M is Hf or Zr;
R 1 is a hydrogen, an optionally substituted hydrocarbyl group, or an optionally substituted heteroatom containing hydrocarbyl group;
each R 2 is independently an optionally substituted hydrocarbyl group, or an optionally substituted heteroatom containing hydrocarbyl group;
each of A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 , A 10 , A 11 and A 12 is a hydrogen, a halide, an optionally substituted hydrocarbyl group, or an optionally substituted heteroatom containing hydrocarbyl group;
L is an optionally substituted bivalent hydrocarbyl group, or an optionally substituted bivalent heteroatom containing hydrocarbyl group;
optionally two or more adjacent A groups may be part of a ring structure; and each X is independently an activatable leaving group; and
ii) a catalyst activator.