Olefin oligomerization and polymerization catalysts
AssigneeEastman Chemical Company
InventorsGino Georges Lavoie, James Allen Ponasik, Jr., Christopher Moore Killian, Leslie Shane Moody, Peter Borden Mackenzie
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Abstract
Disclosed herein are compounds and processes useful for the oligomerization and polymerization of olefins. Transition metal catalyst complexes of groups 7 through 10 with tridentate ligands are described, along with a representative polymerization of ethylene using one of the cobalt complexes. The transition metal complexes of the invention may also be attached to a solid support and used in gas phase processes.
Claims34
A process for the preparation of polyolefins, which comprises contacting one or more monomers of the formula R′CH=CHR″ with a transition metal complex of the formula (I):
- wherein R′, R″ are H, hydrocarbyl or substituted hydrocarbyl, and may be linked to form a cyclic olefin;
- M is Co(II), Co(III), Fe(II), Fe(III), Ru(II), Ru(III), Mn(II) or Mn(III);
- T is H, hydrocarbyl, substituted hydrocarbyl, or other group capable of inserting an olefin;
- L is an olefin or a neutral base, said base having a donating atom, where the donating atom is nitrogen, oxygen, or sulfur capable of being displaced by an olefin;
- in addition, T and L may be taken together to form a π-allyl or a π-benzyl group;
- A− is a weakly coordinating anion;
- and
- X, Y, and Z are selected from various functional groups or combinations of such functional groups selected from the group consisting of
- wherein R1, R2, R3, R4, R5, R6, R7 are each independently H, hydrocarbyl, substituted hydrocarbyl, a heteroatom connected monoradical wherein the connected heteroatom is selected from the group consisting of elements of Group 15 and 16, and silicon, and may also be linked by a bridging hydrocarbyl group or to one another or to R20-R23 to form a covalent bond;
- R20, R21, R22 and R23 are each independently hydrocarbyl, substituted hydrocarbyl or silyl, and may also be linked to R1-R7 to form a covalent bond;
- E is either O or S;
- G1, G2, and G3 are independently C or N, provided that when G1, G2, and G3 are N, only hydrocarbyl and substituted hydrocarbyl substituents are covalently bound to N, and further provided that the octet rule is satisfied in said atom;
- G4 and G5 are independently C, N, O, or S, provided that when they are O, N, and S, only hydrocarbyl and substituted hydrocarbyl substituents are covalently bound to O, N or S, and further provided that the octet rule is satisfied in said atom;
- further provided that X, Y and Z are taken together to form groups of a formula other than the formula
- wherein R31, R32, R33, R34 and R35 are each independently H, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, or substituted heterohydrocarbyl, or an inert functional group;
- and
- R36 and R37 are aryl, substituted aryl, H, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, or substituted heterohydrocarbyl.
A process for the polymerization of olefins which comprises contacting one or more monomers of the formula R′CH=CHR″ with a transition metal catalyst, wherein said catalyst is formed by combining a first compound D, which is a neutral Lewis acid that is capable of abstracting Q− or W− to form a weakly coordinating anion, or a cationic Lewis acid whose counterion is a weakly coordinating anion, or a Brønsted acid whose conjugate base is a weakly coordinating anion, with a second compound of the formula (II):
- wherein R′, R″ are H, hydrocarbyl or substituted hydrocarbyl, and may be linked to form a cyclic olefin;
- Q is hydrocarbyl, chloride, iodide, bromide, substituted hydrocarbyl, hydroxide, alkoxide, amide, nitrate or sulphonate or other group capable of being abstracted by compound D, which is a neutral Lewis acid that is capable of abstracting Q− or W− to form a weakly coordinating anion, or a cationic Lewis acid whose counterion is a weakly coordinating anion, or a Brønsted acid whose conjugate base is a weakly coordinating anion;
- W is hydrocarbyl, chloride, iodide, bromide, substituted hydrocarbyl, hydroxide, alkoxide, amide, nitrate or sulphonate or other group capable of inserting an olefin;
- M is Co(II), Co(III), Fe(II), Fe(III), Ru(II), Ru(III), Mn(II) or Mn(III);
- and
- X, Y, and Z are selected from various functional groups or combinations of such functional groups selected from the group consisting of
- wherein R1, R2, R3, R4, R5, R6, R7 are each independently H, hydrocarbyl, substituted hydrocarbyl, a heteroatom connected monoradical wherein the connected heteroatom is selected from the group consisting of elements of Group 15 and 16, and silicon, and may also be linked by a bridging hydrocarbyl group or to one another or to R20-R23 to form a covalent bond;
- R20, R21, R22, and R23 are each independently hydrocarbyl, substituted hydrocarbyl or silyl, and may also be linked to R1-R7 to form a covalent bond;
- E is either O or S;
- G1, G2, and G3 are independently C or N, provided that when they are N, only hydrocarbyl and substituted hydrocarbyl subtituents are covalently bound to N, and further provided that the octet rule is satisfied in said atom;
- And G4 and G5 are independently C, N, O, or S, provided that when they are O, N, and S, only hydrocarbyl and substituted hydrocarbyl substituents are covalently bound to O, N or S, and further provided that the octet rule is satisfied in said atom;
- further provided that X, Y and Z are taken together to form groups of a formula other than the formula
- wherein R31, R32, R33, R34 and R35 are each independently H, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, or substituted heterohydrocarbyl, or an inert functional group;
- and
- R36 and R37 are aryl, substituted aryl, H, halogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, or substituted heterohydrocarbyl.
Dependencies are inferred from the claim text.