Catalysts containing N-pyrrolyl substituted nitrogen donors
AssigneeEastman Chemical Company
InventorsLeslie Shane Moody, Peter Borden Mackenzie, Christopher Moore Killian, Gino Georges Lavoie, James Allen Ponasik JR., Anthony Gerard Martin Barrett, Thomas William Smith, Jason Clay Pearson
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Abstract
Catalyst compositions useful for the polymerization or oligomerization of olefins are disclosed. Certain of the catalyst compositions comprise N-pyrrolyl substituted nitrogen donors. Also disclosed are processes for the polymerization or oligomerization of olefins using the catalyst compositions.
Claims74
A catalyst composition for the polymerization or oligomerization of olefins, comprising a metal complex ligated by a monodentate, bidentate, tridentate, or tetradentate ligand, wherein at least one of the donor atoms of the ligand is a nitrogen atom substituted by a 1-pyrrolyl or substituted 1-pyrrolyl group;
- wherein:
- the remaining donor atoms of the ligand are selected from the group consisting of C, N, P, As, O, S, and Se;
- and wherein
- said metal in said metal complex is selected from the group consisting of Sc, Ta, Ti, Zr, Hf, V, Nb, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Cu, Pd, Pt, Al, and Ga.
A compound selected from Set 2:
- 114 115 116
- wherein:
- R2x,y are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl;
- silyl, boryl, or ferrocenyl;
- in addition, R2x and R2y may be linked by a bridging group;
- R3a-h are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl, boryl, fluoro, chloro, bromo, cyano, or nitro;
- in addition, any two of R3a-h may be linked by a bridging group.
A catalyst composition for the polymerization or oligomerization of olefins, comprising either (i) a cationic Group 8-10 transition metal complex of a neutral bidentate ligand selected from Set 3, or a tautomer thereof, and a weakly coordinating anion X−, or (ii) the reaction product of Ni(1,5-cyclooctadiene)2, B(C6F5)3, one or more olefin monomers, and a neutral bidentate ligand selected from Set 3:
- 117 118 119 120 121 122 123 124 125 126 127 128 129 130
- wherein:
- R2a-f,x-z are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connected substituted hydrocarbyl;
- R2a-f may also be silyl, boryl, or ferrocenyl;
- in addition, any two of R2a-d, or R2x and R2y, may be linked by a bridging group;
- R3a-j are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl, boryl, fluoro, chloro, bromo, cyano, or nitro;
- in addition, any two of R3a-j may be linked by a bridging group;
- R4a and R4b are each independently hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connected substituted hydrocarbyl;
- in addition, R4a and R4b may be linked by a bridging group;
- G1 is hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connected substituted hydrocarbyl;
- G1, C, and N collectively comprise a 5- or 6-membered heterocyclic ring;
- G2 is hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connected substituted hydrocarbyl;
- G2, V1, N, and N collectively comprise a 5- or 6-membered heterocyclic ring;
- V1 is CR3j, N, or PR4aR4b;
- E1 is O, S, Se, or NR2e;
- E2 and E3 are O, S, or NR2e;
- and
- Q is C—R3j, PR4aR4b, S(E2)(NR2eR2f) or S(E2)(E3R2e);
- provided that the ligand is not of the formula a15.
A ligand selected from Set 4:
- 131 132 133 134 135 136 137
- wherein:
- R2a-f,x-z are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connected substituted hydrocarbyl;
- R2a-f may also be silyl, boryl, or ferrocenyl;
- in addition, any two of R2a-d, or R2x and R2y, may be linked by a bridging group;
- R3a-j are each independently H, hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, heteroatom connected substituted hydrocarbyl, fluoroalkyl, silyl, boryl, fluoro, chloro, bromo, cyano, or nitro;
- in addition, any two of R3a-j may be linked by a bridging group;
- R4a and R4b are each independently hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connected substituted hydrocarbyl;
- in addition, R 4a and R4b may be linked by a bridging group;
- G1 is hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connected substituted hydrocarbyl;
- G1, C, and N collectively comprise a 5- or 6-membered heterocyclic ring;
- G2 is hydrocarbyl, substituted hydrocarbyl, heteroatom connected hydrocarbyl, or heteroatom connected substituted hydrocarbyl;
- G2, V1, N, and N collectively comprise a 5- or 6-membered heterocyclic ring;
- V1 is CR3j, N, or PR4aR4b;
- E1 is O, S, Se, or NR2e;
- E2 and E3 are O, S, or NR2e;
- and
- Q is C—R3j, PR4aR4b, S(E2)(NR2eR2f) or S(E2)(E3R2e);
- provided that (i) the ligand is not of the formula a15, (ii) when the ligand is of the formula b7, and E3 is O, R3a-d are H, and R2x is H, the pyrrolyl group is other than N-carbazolyl, N-(3-phenylindenyl) or unsubstituted N-pyrrolyl, and (iii) when the ligand is of formula a55, it is other than carbazol-9-yl-quinolin-2-ylmethylene-amine.
A process for the polymerization or oligomerization of olefins, comprising contacting a Group 8-10 transition metal catalyst composition with one or more olfins, wherein said catalyst composition exhibits improved thermal stability, wherein said metal complex comprises a bidentate or variable denticity ligand comprising one or two nitrogen donor atom or atoms substituted by an aromatic or heteroaromatic ring, and wherein the ortho positions of said ring are substituted by groups other than H or alkyl;
- provided that at least one of the ortho positions of at least one of said aromatic or heteroaromatic rings is substituted by an aryl or heteroaryl group.
A process for the polymerization or oligomerization of olefins, comprising contacting a Group 8-10 transition metal catalyst composition with one or more olefins, wherein said catalyst composition exhibits improved stability in the presence of an amount of hydrogen effective to achieve chain transfer, wherein said metal complex comprises a bidentate or variable denticity ligand comprising one or two nitrogen donor atom or atoms substituted by an aromatic or heteroaromatic ring, and wherein the ortho positions of said ring are substituted by groups other than H or alkyl.
A process for the polymerization or oligomerization of olefins, comprising contacting a Group 8-10 transition metal catalyst composition with one or more olefins, wherein said catalyst composition exhibits either improved thermal stability, or exhibits improved stability in the presence of an amount of hydrogen effective to achieve chain transfer, or both, wherein said metal complex comprises a bidentate or variable denticity ligand comprising one or two nitrogen donor atom or atoms substituted by an aromatic or heteroaromatic ring, wherein at least one of the ortho positions of at least one of said aromatic or heteroaromatic rings is substituted by an aryl or heteroaryl group which is capable of reversibly forming an agostic bond to said Group 8-10 transition metal under olefin polymerization reaction conditions.
A process for the polymerization or oligomerization of olefins, comprising contacting a Group 8-10 transition metal catalyst composition with one or more olefins, wherein said catalyst composition exhibits either improved thermal stability, or exhibits improved stability in the presence of an amount of hydrogen effective to achieve chain transfer, or both, wherein said composition comprises a bidentate or variable denticity ligand comprising one or two nitrogen donor atom or atoms substituted by an aromatic or heteroaromatic ring, wherein the ortho positions of said ring are substituted by groups other than H or alkyl;
- provided that at least one of the ortho positions of at least one of said aromatic or heteroaromatic ring is substituted by an aryl or heteroaryl group.
Dependencies are inferred from the claim text.