Catalyst systems and polymerization processes for using the same
A catalyst system including the product of the combination of an unbridged Group 4 metallocene compound and a 2,6-bis(imino)pyridyl iron complex is provided. A process for the polymerization of monomers (such as olefin monomers) and a polymer produced therefrom are also provided.
1. A catalyst system comprising the product of the combination of: a Group 4 metallocene catalyst represented by formula (I):
wherein:
M is a group 4 metal,
X 1 and X 2 are independently a univalent anionic ligand, a diene ligand, an alkylidene ligand, or X 1 and X 2 are joined to form a metallocyclic ring, and further wherein:
R 1 ,R 2 , R 3 , and R 4 are each hydrogen and R 5 is R**—SiR* 3 where each R* is independently C 1 to C 20 substituted or unsubstituted hydrocarbyl, and R** is C 1 to C 4 hydrocarbyl;
each of R 6 , R 13 , R 14 , R 15 , and R 16 is independently selected from hydrogen, halogen, C 1 -C 40 hydrocarbyl, substituted C 1 -C 40 hydrocarbyl, —NR′ 2 , —SR′, —OR′, —OSiR′ 3 , or —PR′ 2 , wherein each R′ is independently hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl, or one or more of R 14 and R 15 , and R 15 and R 16 are joined to form a saturated ring, unsaturated ring, substituted saturated ring, or substituted unsaturated ring;
each of R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 is independently selected from hydrogen, halogen, C 1 -C 40 hydrocarbyl, substituted C 1 -C 40 hydrocarbyl, aryl, substituted aryl, —NR′ 2 , —SR′, —OR′, —OSiR′ 3 , or —PR′ 2 , wherein each R′ is independently hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl, or one or more of R 7 and R 8 , R 8 and R 10 , and R 10 and R 12 are joined to form a saturated ring, unsaturated ring, substituted saturated ring, or substituted unsaturated ring; and
an iron catalyst represented by formula (II):
wherein:
R 6a and R 15a are independently halogen, —CF 3 , hydrogen, or C 1 -C 22 -alkyl, or —OR′, each of R 1a and R 2a is independently hydrogen, C 1 -C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 -aryl, arylalkyl wherein alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, or five-, six- or seven-membered heterocyclyl comprising at least one atom selected from N, P, O and S, wherein each of R 1a and R 2a is optionally substituted by halogen, —NR′ 2 , —OR′ or —SiR″ 3 , wherein R 1a optionally bonds with R 3a , and R 2a optionally bonds with R 5a , in each case to independently form a five-, six- or seven-membered ring,
each of R 3a , R 4a , R 5a , R 7a , R 8a , R 9a , R 10a , R 11a , R 12a , R 13a , and R 14a is independently hydrogen, C 1 -C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 -aryl, arylalkyl wherein alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, —NR′ 2 , —OR′, halogen, —SiR″ 3 or five-, six- or seven-membered heterocyclyl comprising at least one atom selected from N, P, O and S;
wherein each of R 3a , R 4a , R 5a , R 7a , R 8a , R 9a , R 10a , R 11a , R 12a , R 13a , and R 14a is independently optionally substituted by halogen, —NR′ 2 , —OR′ or —SiR″ 3 , X 1a and X 2a are independently halogen, hydrogen, C 1 -C 20 -alkyl, C 2 -C 10 -alkenyl, C 6 -C 20 -aryl, arylalkyl wherein alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, —NR′ 2 , —OR′, —SR′, —SO 3 R′, —OC(O)R′, —CN, —SCN, β-diketonate, —CO, —BF 4 − , —PF 6 − or bulky non-coordinating anion, or X 1a and X 2a optionally bond to form a five- or six-membered ring,
each R′ is independently hydrogen, C 1 -C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 -aryl, arylalkyl wherein alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, or —SiR″ 3 , wherein R′ is optionally substituted by halogen or nitrogen- or oxygen-containing groups, or two R′ radicals optionally bond to form a five- or six-membered ring, each R″ is independently hydrogen, C 1 -C 22 -alkyl, C 2 -C 22 -alkenyl, C 6 -C 22 -aryl, arylalkyl wherein alkyl has from 1 to 10 carbon atoms and aryl has from 6 to 20 carbon atoms, wherein each R″ is optionally substituted by halogen or nitrogen- or oxygen-containing groups, or two R″ radicals optionally bond to form a five- or six-membered ring.
2. The catalyst system of claim 1 , wherein a molar ratio of the group 4 metallocene catalyst to the iron catalyst is from 1:1 to 20:1.
3. The catalyst system of claim 1 , wherein M is hafnium.
4. The catalyst system of claim 1 , wherein each of R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 is hydrogen.
5. The catalyst system of claim 1 , wherein R 5 is —CH 2 —Si—(CH 3 ) or —CH 2 —Si—(CH 2 CH 3 ) 3 .
6. The catalyst system of claim 1 , wherein each of R 14 , R 15 , and R 16 is hydrogen.
7. The catalyst system of claim 1 , wherein X 1 and X 2 are chloride.
8. The catalyst system of claim 1 , wherein the group 4 metallocene catalyst is one or more of:
9. The catalyst system of claim 8 , wherein the group 4 metallocene catalyst is one or more of:
10. The catalyst system of claim 1 , wherein R 6a and R 15a are independently fluorine, chlorine, bromine, or iodine.
11. The catalyst system of claim 10 , wherein R 6a and R 15a are chlorine.
12. The catalyst system of claim 1 , wherein R 1a and R 2a are independently C 1 -C 22 -alkyl, substituted C 1 -C 22 -alkyl, unsubstituted phenyl, or substituted phenyl.
13. The catalyst system of claim 12 , wherein each of R 1a and R 2a is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, n-heptyl, isoheptyl, sec-heptyl, tert-heptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, n-nonyl, isononyl, sec-nonyl, tert-nonyl, n-decyl, isodecyl, sec-decyl, and tert-decyl.
14. The catalyst system of claim 1 , wherein each of R 8a , R 10a , R 11a , and R 13a is independently selected from C 1 -C 22 -alkyl, wherein each of R 8a , R 10a , R 11a , and R 13a is independently optionally substituted by halogen, —NR′ 2 , —OR′ or —SiR″ 3 .
15. The catalyst system of claim 1 , wherein each of R 7a , R 9a , R 12a , and R 14a is hydrogen.
16. The catalyst system of claim 1 , wherein each of R 3a , R 4a , and R 5a is hydrogen.
17. The catalyst system of claim 1 , wherein X 1a and X 2a are chlorine.
18. The catalyst system of claim 1 , wherein the iron catalyst is one or more of:
19. The catalyst system of claim 18 , wherein the iron catalyst is one or more of:
20. The catalyst system of claim 1 , further comprising an activator.
21. The catalyst system of claim 1 , further comprising a support material.
22. A process for polymerization of olefin monomers comprising:
contacting one or more monomers with a catalyst system of claim 1 ; and
obtaining a polyolefin composition.