Transition metal compounds for olefin polymerization and oligomerization

A transition metal catalyst compound represented by the formula (I):

• where:
• M and M′ are, independently, a group 8, 9, 10 or 11 transition metal;
• each R group is, independently, is, hydrogen, or a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituents, and optionally, adjacent R groups may join together to form a substituted or unsubstituted, saturated, partially unsaturated, or aromatic cyclic or polycyclic substituent;
• R′ is hydrogen, or a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituents, and optionally, adjacent R groups may join together with R′ to form a substituted or unsubstituted, saturated, partially unsaturated, or aromatic cyclic or polycyclic substituent;
• each X group is, independently, is, hydrogen, a halogen, or a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituents, and optionally, adjacent X groups may join together to form a substituted or unsubstituted, saturated, partially unsaturated, or aromatic cyclic or polycyclic substituent;
• m and m′ are, independently, 0, 1, 2, or 3;
• z and z′ are, independently, 1, 2, or 3;
• N is nitrogen;
• Q is hydrogen, or a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituents;
• Q′ is hydrogen, or a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituents;
• and
• L is selected from the group consisting of:
• 1) a monoaryl unit unsubstituted, partially substituted or fully substituted with a number of R substituents on the ring,
• 2) a fused aryl unit selected from the group consisting of the C10 to C22 fused aromatic hydrocarbyl units, unsubstituted, partially substituted or fully substituted with a number of R substituents on the ring,
• 3) two aryl units bridged by a substituted or unsubstituted alkyl group, where the aryl units may be unsubstituted, partially substituted or fully substituted with a number of R substituents on the ring,
• 4) two aryl units bridged by an unsaturated hydrocarbon group, where the aryl units may be unsubstituted, partially substituted or fully substituted with a number of R substituents on the ring,
• 5) two aryl rings bridged by a fused aryl unit selected from the fused aryl units having ten or more carbon atoms, unsubstituted, partially substituted or fully substituted with a number of R substituents on of the rings,
• 6) two aryl rings bridged by a polyaryl unit in which the polyaryl unit is selected from the group consisting of one or more aromatic rings, unsubstituted, partially substituted or fully substituted with a number of R substituents on the rings,
• 7) two aryl rings bridged by a methylene unit in which the methylene unit contains one or two R groups and where the aryl units may be unsubstituted, partially substituted or fully substituted with a number of R substituents on the ring,
• 8) two diaryl units bridged by a heteroatom X (X═O, NR, PR, S, BR, AlR, SiR2) in which a number of R substituents may be on the heteroatom and where the aryl units may be unsubstituted, partially substituted or fully substituted with a number of R substituents on the ring,
• 9) two aryl units bridged by a heteroatom or hetroatom-containing fragment X (X′O, NR, PR, S, BR, AlR, SiR2) and one or more hydrocarbon sections, selected from the group consisting of C1 to C30 hydrocarbyls, C1 to C30 substituted phenyls, and where the aryl units may be unsubstituted, partially substituted or fully substituted with a number of R substituents on the ring,
• 10) two aryl units bridged by one or more 5-, 6- or 7-membered heterocyclic rings containing one or more heteroatoms X (X═O, NR, BR), where the internal rings can be unsubstituted, partially substituted or fully substituted and saturated, partially unsaturated or aromatic,
• 11) two aryl units bridged by a metallocene section in which the aromatic rings can be unsubstituted, partially substituted or fully substituted with a number of R substituents on the aryl or the cyclopentadienyl and the metal is selected from Group 4 to Group 9 of the Periodic Table, and
• 12) two aryl units bridged by an α-diimine, a iminopyridine, a bis(imino)pyridine or a polypyridine group coordinated to a metal dihalide where the metal is selected from Group 8 to Group 11 of the Periodic Table, where the imino carbons or the pyridine rings can be unsubstituted, partially substituted or fully substituted with a number of R substituents, and α where the aryl units may be unsubstituted, partially substituted or fully substituted with a number of R substituents on the ring on various positions of the aryl, where each R group is, independently, selected from the group consisting of a hydrogen, a halogen, C1 to C30 hydrocarbyls, and C1 to C30 substituted phenyls.

A catalyst system comprising activator and a transition metal catalyst compound represented by the formula (I):

• where:
• M and M′ are, independently, a group 8, 9, 10 or 11 transition metal;
• each R group is, independently, is, hydrogen, or a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituents, and optionally, adjacent R groups may join together to form a substituted or unsubstituted, saturated, partially unsaturated, or aromatic cyclic or polycyclic substituent;
• R′ is hydrogen, or a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituents, and optionally, adjacent R groups may join together with R′ to form a substituted or unsubstituted, saturated, partially unsaturated, or aromatic cyclic or polycyclic substituent;
• each X group is, independently, is, hydrogen, a halogen, or a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituents, and optionally, adjacent X groups may join together to form a substituted or unsubstituted, saturated, partially unsaturated, or aromatic cyclic or polycyclic substituent;
• m and m′ are, independently, 0, 1, 2, or 3;
• z and z′ are, independently, 1, 2, or 3;
• N is nitrogen;
• Q is hydrogen, or a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituents;
• Q′ is hydrogen, or a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituents;
• and
• L is a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituent, provided however that when M and M′ are Ni or M and M′ are Pd, then L is selected from the group consisting of aryl groups represented by the formulae:
• where the dashed lines indicate the bonds to the nitrogen atoms in the formula (I) above,
• X in formula 14 is O, NR, PR, S, BR, AlR, SiR2;
• T=O, NR, BR
• each R group is in formula 3, 4, 6, 7, 8, 9, 10, 11, 12, 13 and 14, independently, selected from the group consisting of hydrogen, halogen, C1 to C30 hydrocarbyls, and C1 to C30 substituted phenyls;
• M1 in formula 13 is a transition metal selected from Groups 4 to 9;
• M2 in formula 14 is a transition metal selected from Groups 8 to 11;
• and
• M3 in formula 14 is a transition metal selected from Groups 8 to 11.

A method to polymerize unsaturated monomers comprising contacting one or more monomers with a catalyst system comprising an activator and a transition metal catalyst compound represented by the formula (I):

• where:
• M and M′ are, independently, a group 8, 9, 10 or 11 transition metal;
• each R group is, independently, is, hydrogen, or a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituents, and optionally, adjacent R groups may join together to form a substituted or unsubstituted, saturated, partially unsaturated, or aromatic cyclic or polycyclic substituent;
• R′ is hydrogen, or a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituents, and optionally, adjacent R groups may join together with R′ to form a substituted or unsubstituted, saturated, partially unsaturated, or aromatic cyclic or polycyclic substituent;
• each X group is, independently, is, hydrogen, a halogen, or a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituents, and optionally, adjacent X groups may join together to form a substituted or unsubstituted, saturated, partially unsaturated, or aromatic cyclic or polycyclic substituent;
• m and m′ are, independently, 0, 1, 2, or 3;
• z and z′ are, independently, 1, 2, or 3;
• N is nitrogen;
• Q is hydrogen, or a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituents;
• Q′ is hydrogen, or a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituents;
• and
• L is a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituent, provided however that when M and M′ are Ni or M and M′ are Pd, then L is selected from the group consisting of aryl groups represented by the formulae:
• where the dashed lines indicate the bonds to the nitrogen atoms in the formula (I) above, X in formula 14 is O, NR, PR, S, BR, AlR, SiR2;
• T=O, NR, BR
• each R group is in formula 3, 4, 6, 7, 8, 9, 10, 11, 12, 13 and 14, independently, selected from the group consisting of hydrogen, halogen, C1 to C30 hydrocarbyls, and C1 to C30 substituted phenyls;
• M1 in formula 13 is a transition metal selected from Groups 4 to 9;
• M2 in formula 14 is a transition metal selected from Groups 8 to 11;
• and
• M3 in formula 14 is a transition metal selected from Groups 8 to 11.

A method to oligomerize an unsaturated monomer comprising contacting one or more monomers with a catalyst system comprising an activator and a transition metal catalyst compound represented by the formula (I):

• where:
• M and M′ are, independently, a group 8, 9, 10 or 11 transition metal;
• each R group is, independently, is, hydrogen, or a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituents, and optionally, adjacent R groups may join together to form a substituted or unsubstituted, saturated, partially unsaturated, or aromatic cyclic or polycyclic substituent;
• R′ is hydrogen, or a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituents, and optionally, adjacent R groups may join together with R′ to form a substituted or unsubstituted, saturated, partially unsaturated, or aromatic cyclic or polycyclic substituent;
• each X group is, independently, is, hydrogen, a halogen, or a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituents, and optionally, adjacent X groups may join together to form a substituted or unsubstituted, saturated, partially unsaturated, or aromatic cyclic or polycyclic substituent;
• m and m′ are, independently, 0, 1, 2, or 3;
• z and z′ are, independently, 1, 2, or 3;
• N is nitrogen;
• Q is hydrogen, or a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituents;
• Q′ is hydrogen, or a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituents;
• and
• L is a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl, or substituted germylcarbyl substituent, provided however that when M and M′ are Ni or M and M′ are Pd, then L is selected from the group consisting of aryl groups represented by the formulae:
• where the dashed lines indicate the bonds to the nitrogen atoms in the formula (I) above, X in formula 14 is O, NR, PR, S, BR, AlR, SiR2;
• T=O, NR, BR
• each R group is in formula 3, 4, 6, 7, 8, 9, 10, 11, 12, 13 and 14, independently, selected from the group consisting of hydrogen, halogen, C1 to C30 hydrocarbyls, and C1 to C30 substituted phenyls;
• M1 in formula 13 is a transition metal selected from Groups 4 to 9;
• M2 in formula 14 is a transition metal selected from Groups 8 to 11;
• and
• M3 in formula 14 is a transition metal selected from Groups 8 to 11.