Pyridyldiamido transition metal complexes, production and use thereof
Pyridyldiamido transition metal complexes are disclosed for use in alkene polymerization to produce multimodal polyolefins.
1. A pyridyldiamido transition metal complex having the general formula (A) or (B):
wherein:
M is a Group 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 metal;
Q 1 is a group that links R 2 and Z by a three atom bridge with the central of the three atoms being a group 15 or 16 element represented by the formula: -G 1 -G 2 -G 3 - where G 2 is a group 15 or 16 atom, G 1 and G 3 are each a group 14, 15 or 16 atom, where G 1 , G 2 , and G 3 , or G 1 and G 2 , or G 1 and G 3 , or G 2 and G 3 may form a singular or multi ring system, and if any of G 1 and/or G 3 is a group 14 atom then R 30 and R 31 are bound to such G atom(s), and if any of G 1 , G 2 , and/or G 3 is a group 15 atom then R 30 is bound to such G atom(s), where each R 30 and R 31 is, independently, hydrogen or a C 1 to C 100 hydrocarbyl group;
Q 2 is a group that forms an anionic bond with M, said Q 2 group being selected from O, S, Se, Te, Po, NR 17 or PR 17 , where R 17 is selected from hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, aryloxy, halogen, amino, and silyl;
Q 3 is -(TT)- or -(TTT)-, where each T is carbon or a heteroatom and said carbon or heteroatom may be unsubstituted or substituted with one or more R 30 groups that together with the “—C-Q 3 =C—” fragment, forms a 5- or 6-membered cyclic group or a polycyclic group including the 5- or 6-membered cyclic group, where each R 30 group is, independently, hydrogen or a C 1 to C 100 hydrocarbyl group;
R 1 is selected from the group consisting of hydrocarbyls, and substituted hydrocarbyls, or silyl groups;
R 2 and R 10 are each, independently, -E(R 12 )(R 13 )— with E being carbon, silicon, or germanium, and each R 12 and R 13 being independently selected from the group consisting of hydrogen, hydrocarbyls, and substituted hydrocarbyls, alkoxy, silyl, amino, aryloxy, halogen, and phosphino, R 12 and R 13 may be joined to form a saturated, substituted or unsubstituted hydrocarbyl ring, where the ring has 4, 5, 6, or 7 ring carbon atoms and where substitutions on the ring can join to form additional rings, or R 12 and R 13 may be joined to form a saturated heterocyclic ring, or a saturated substituted heterocyclic ring where substitutions on the ring can join to form additional rings;
Z is —(R 14 ) p C—C(R 15 ) q —, where R 14 and R 15 are independently selected from the group consisting of hydrogen, hydrocarbyls, and substituted hydrocarbyls, and wherein adjacent R 14 and R 15 groups may be joined to form an aromatic or saturated, substituted or unsubstituted hydrocarbyl ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings;
p is 1 or 2;
q is 1 or 2;
L is an anionic leaving group, where the L groups may be the same or different and any two L groups may be linked to form a dianionic leaving group;
n is 0, 1, 2, 3, or 4;
L′ is neutral Lewis base;
w is 0, 1, 2, 3, or 4; and
wherein n+w is no greater than 4;
provided that one of R 2 and R 10 is asymmetrically substituted and the other is symmetrically substituted.
2. A pyridyldiamido transition metal complex represented by the formula (I) or (II):
wherein:
M is a Group 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 metal;
R 1 and R 11 are independently selected from the group consisting of hydrocarbyls, and substituted hydrocarbyls, or silyl groups;
R 2 and R 10 are each, independently, -E(R 12 )(R 13 )— with E being carbon, silicon, or germanium, and each R 12 and R 13 being independently selected from the group consisting of hydrogen, hydrocarbyls, and substituted hydrocarbyls, alkoxy, silyl, amino, aryloxy, halogen, and phosphino, R 12 and R 13 may be joined to form a saturated, substituted or unsubstituted hydrocarbyl ring, where the ring has 4, 5, 6, or 7 ring carbon atoms and where substitutions on the ring can join to form additional rings, or R 12 and R 13 may be joined to form a saturated heterocyclic ring, or a saturated substituted heterocyclic ring where substitutions on the ring can join to form additional rings;
R 3 , R 4 , and R 5 are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, aryloxy, halogen, amino, and silyl, and wherein adjacent R groups (R 3 & R 4 and/or R 4 & R 5 ) may be joined to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings;
R 6 , R 7 , R 8 , R 9 , R 15 , and R 16 are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen, amino, and silyl, and wherein adjacent R groups (R 6 & R 7 , and/or R 7 & R 15 , and/or R 16 & R 15 , and/or R 8 & R 9 ) may be joined to form a saturated, substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings;
L is an anionic leaving group, where the L groups may be the same or different and any two L groups may be linked to form a dianionic leaving group;
n is 0, 1, 2, 3, or 4;
L′ is neutral Lewis base;
w is 0, 1, 2, 3, or 4; and
wherein n+w is no greater than 4;
provided that one of R 2 and R 10 is asymmetrically substituted and the other is symmetrically substituted.
3. The complex of claim 1 or 2 , wherein M is Ti, Zr, or Hf.
4. The complex of claim 1 or 2 , wherein R 2 is represented by the formula:
where R 12 is hydrogen, alkyl, aryl, or halogen; and R 13 is hydrogen, alkyl, aryl, or halogen.
5. The complex of claim 2 , wherein R 6 , R 7 , R 8 , R 9 , R 15 , and R 16 , are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen, amino, and silyl.
6. The complex of claim 2 , wherein R 1 , R 3 , R 4 , R 5 , R 11 each contain from 1 to 30 carbon atoms.
7. The complex of claim 2 , wherein E is carbon and R 1 and R 11 are independently selected from phenyl groups that are substituted with 0, 1, 2, 3, 4, or 5 substituents selected from the group consisting of F, Cl, Br, I, CF 3 , NO 2 , alkoxy, dialkylamino, hydrocarbyl, and substituted hydrocarbyls groups with from one to ten carbons.
8. The complex of claim 1 or 2 , wherein each L is independently selected from the group consisting of halide, alkyl, aryl, alkoxy, amido, hydrido, phenoxy, hydroxy, silyl, allyl, alkenyl, and alkynyl.
9. The complex of claim 1 or 2 , wherein each L′ is independently selected from the group consisting of ethers, thio-ethers, amines, nitriles, imines, pyridines, and phosphines.
10. The complex of claim 1 or 2 , wherein for R 10 , E is carbon, R 12 is phenyl, and R 13 is H.
11. The complex of claim 1 or 2 , wherein the R 2 group(s) are selected from the group consisting of CH 2 , CMe 2 , SiMe 2 , SiEt 2 , SiPr 2 , SiBu 2 , SiPh 2 , Si(aryl) 2 , and Si(alkyl) 2 , CH(aryl), CH(Ph), CH(alkyl), CH(2-isopropylphenyl), where alkyl is a C 1 to C 40 alkyl group, aryl is a C 5 to C 40 aryl group.
12. The complex of claim 1 or 2 , wherein the R 10 group(s) are selected from the group consisting of CH 2 , CMe 2 , SiMe 2 , SiEt 2 , SiPr 2 , SiBu 2 , SiPh 2 , Si(aryl) 2 , and Si(alkyl) 2 , CH(aryl), CH(Ph), CH(alkyl), CH(2-isopropylphenyl), where alkyl is a C 1 to C 40 alkyl group, aryl is a C 5 to C 40 aryl group, and Ph is phenyl.
13. The complex of claim 1 or 2 , wherein R 2 is one or more of CH 2 and CMe 2 , and R 10 is one or more of CH(Ph), CH(aryl), and CH(alkyl), where alkyl is a C 1 to C 40 alkyl group, aryl is a C 5 to C 40 aryl group, and Ph is phenyl.
14. The complex of claim 1 or 2 , wherein R 2 and R 10 groups (expressed as R 2 & R 10 are: (CH 2 & CH(Ph)), (CMe 2 and CH(Ph)), (CH 2 and CH(aryl)), (CH 2 and CH(alkyl)), where alkyl is a C 1 to C 40 alkyl group, aryl is a C 5 to C 40 aryl group and Ph is phenyl.
15. A catalyst system comprising an activator and a pyridyldiamido transition metal complex represented by the formula (A) or (B):
wherein:
M is a Group 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 metal;
Q 1 is a group that links R 2 and Z by a three atom bridge with the central of the three atoms being a group 15 or 16 element represented by the formula: -G 1 -G 2 -G 3 - where G 2 is a group 15 or 16 atom, G 1 and G 3 are each a group 14, 15 or 16 atom, where G 1 , G 2 , and G 3 , or G 1 and G 2 , or G 1 and G 3 , or G 2 and G 3 may form a singular or multi ring system, and if any of G 1 and/or G 3 is a group 14 atom then R 30 and R 31 are bound to such G atom(s), and if any of G 1 , G 2 , and/or G 3 is a group 15 atom then R 30 is bound to such G atom(s), where each R 30 and R 31 is, independently, hydrogen or a C 1 to C 100 hydrocarbyl group;
Q 2 is a group that forms an anionic bond with M, said Q 2 group being selected from O, S, Se, Te, Po, NR 17 or PR 17 , where R 17 is selected from hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, aryloxy, halogen, amino, and silyl;
Q 3 is -(TT)- or -(TTT)-, where each T is carbon or a heteroatom and said carbon or heteroatom may be unsubstituted or substituted with one or more R 30 groups that together with the “—C-Q 3 =C—” fragment, forms a 5- or 6-membered cyclic group or a polycyclic group including the 5- or 6-membered cyclic group, where each R 30 group is, independently, hydrogen or a C 1 to C 100 hydrocarbyl group;
R 1 is selected from the group consisting of hydrocarbyls, and substituted hydrocarbyls, or silyl groups;
R 2 and R 10 are each, independently, -E(R 12 )(R 13 )— with E being carbon, silicon, or germanium, and each R 12 and R 13 being independently selected from the group consisting of hydrogen, hydrocarbyls, and substituted hydrocarbyls, alkoxy, silyl, amino, aryloxy, halogen, and phosphino, R 12 and R 13 may be joined to form a saturated, substituted or unsubstituted hydrocarbyl ring, where the ring has 4, 5, 6, or 7 ring carbon atoms and where substitutions on the ring can join to form additional rings, or R 12 and R 13 may be joined to form a saturated heterocyclic ring, or a saturated substituted heterocyclic ring where substitutions on the ring can join to form additional rings;
Z is —(R 14 ) p C—C(R 15 ) q —, where R 14 and R 15 are independently selected from the group consisting of hydrogen, hydrocarbyls, and substituted hydrocarbyls, and wherein adjacent R 14 and R 15 groups may be joined to form an aromatic or saturated, substituted or unsubstituted hydrocarbyl ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings;
p is 1 or 2;
q is 1 or 2;
L is an anionic leaving group, where the L groups may be the same or different and any two L groups may be linked to form a dianionic leaving group;
n is 0, 1, 2, 3, or 4;
L′ is neutral Lewis base;
w is 0, 1, 2, 3, or 4; and
wherein n+w is no greater than 4;
provided that one of R 2 and R 10 is asymmetrically substituted and the other is symmetrically substituted.
16. A catalyst system comprising an activator and a pyridyldiamido transition metal complex represented by the formula (I) or (II):
wherein:
M is a Group 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 metal;
R 1 and R 11 are independently selected from the group consisting of hydrocarbyls, and substituted hydrocarbyls, or silyl groups;
R 2 and R 10 are each, independently, -E(R 12 )(R 13 )— with E being carbon, silicon, or germanium, and each R 12 and R 13 being independently selected from the group consisting of hydrogen, hydrocarbyls, and substituted hydrocarbyls, alkoxy, silyl, amino, aryloxy, halogen, and phosphino, R 12 and R 13 may be joined to form a saturated, substituted or unsubstituted hydrocarbyl ring, where the ring has 4, 5, 6, or 7 ring carbon atoms and where substitutions on the ring can join to form additional rings, or R 12 and R 13 may be joined to form a saturated heterocyclic ring, or a saturated substituted heterocyclic ring where substitutions on the ring can join to form additional rings;
R 3 , R 4 , and R 5 are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, aryloxy, halogen, amino, and silyl, and wherein adjacent R groups (R 3 & R 4 and/or R 4 & R 5 ) may be joined to form a substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring atoms and where substitutions on the ring can join to form additional rings;
R 6 , R 7 , R 8 , R 9 , R 15 , and R 16 are independently selected from the group consisting of hydrogen, hydrocarbyls, substituted hydrocarbyls, alkoxy, halogen, amino, and silyl, and wherein adjacent R groups (R 6 & R 7 , and/or R 7 & R 15 , and/or R 16 & R 15 , and/or R 8 & R 9 ) may be joined to form a saturated, substituted or unsubstituted hydrocarbyl or heterocyclic ring, where the ring has 5, 6, 7, or 8 ring carbon atoms and where substitutions on the ring can join to form additional rings;
L is an anionic leaving group, where the L groups may be the same or different and any two L groups may be linked to form a dianionic leaving group;
n is 0, 1, 2, 3, or 4;
L′ is neutral Lewis base;
w is 0, 1, 2, 3 or 4; and
wherein n+w is no greater than 4;
provided that one of R 2 and R 10 is asymmetrically substituted and the other is symmetrically substituted.
17. The catalyst system of claim 15 or 16 , wherein the activator is an alumoxane.
18. The catalyst system of claim 15 or 16 , wherein the activator is a non-coordinating anion.
19. The catalyst system of claim 15 or 16 , wherein the R 2 group(s) are selected from the group consisting of CH 2 , CMe 2 , SiMe 2 , SiEt 2 , SiPr 2 , SiBu 2 , SiPh 2 , Si(aryl) 2 , and Si(alkyl) 2 , CH(aryl), CH(Ph), CH(alkyl), CH(2-isopropylphenyl), and the R 10 group(s) are selected from the group consisting of CH 2 , CMe 2 , SiMe 2 , SiEt 2 , SiPr 2 , SiBu 2 , SiPh 2 , Si(aryl) 2 , and Si(alkyl) 2 , CH(aryl), CH(Ph), CH(alkyl), CH(2-isopropylphenyl), where alkyl is a C 1 to C 40 alkyl group, aryl is a C 5 to C 40 aryl group, and Ph is phenyl.
20. A polymerization process to produce multimodal polyolefin comprising:
a) contacting one or more olefin monomers with the catalyst system of claim 15 or 16 ; and
b) obtaining multimodal olefin polymer.
21. The process of claim 20 , wherein the activator is an alumoxane.
22. The process of claim 20 , wherein the activator is a non-coordinating anion.
23. The process of claim 20 , wherein the monomer comprises ethylene.
24. The process of claim 20 , wherein the monomer comprises propylene.
25. The process of claim 20 , wherein the pyridyldiamido transition metal complex is supported.
26. The pyridyldiamido transition metal complex of claim 1 , wherein T is C, O, S, or N.
27. The catalyst system of claim 15 , wherein T is C, O, S, or N.
28. A polymerization process comprising: a) contacting one or more olefin monomers with the catalyst system of claim 15 or 16 ; and b) obtaining multimodal olefin polymer, wherein the activator is a non-coordinating anion, and the monomer comprises ethylene and propylene.
29. A polymerization process comprising: a) contacting one or more olefin monomers with the catalyst system of claim 15 or 16 ; and b) obtaining multimodal olefin polymer, wherein the activator is a non-coordinating anion, the monomer comprises ethylene and propylene, and the pyridyldiamido transition metal complex is supported.