Catalyst systems including two hafnocene catalyst compounds
The present disclosure relates to dual catalyst systems and processes for use thereof. The present disclosure further provides a catalyst system that is a combination of at least two hafnium metallocene catalyst compounds. The catalyst systems may be used for olefin polymerization processes. The present disclosure further provides for polymers, which can be formed by processes and catalyst systems of the present disclosure.
1. A catalyst system comprising: activator, support material, a hafnium metallocene catalyst represented by formula (I):
wherein:
M is Hf;
each of R 1 , R 2 , R 3 , R 4 R 5 , R 6 , R 7 , and R 8 is independently hydrogen, alkoxide, C 1 to C 40 substituted or unsubstituted hydrocarbyl, or —R 13 —SiR′ 3 or —R 13 —CR′ 3 wherein R 13 is C 1 to C 4 hydrocarbyl, and each R′ is independently hydrogen or C 1 to C 20 substituted or unsubstituted hydrocarbyl, or two or more of R 1 , R 2 , R 3 , and R 4 form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent ring, or two or more of R 5 , R 6 , R 7 , and R 8 form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent ring, wherein at least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 is —R 13 —SiR′ 3 or —R 13 —CR′ 3 wherein R 13 is C 1 to C 4 hydrocarbyl, and each R′ is independently hydrogen or C 1 to C 20 substituted or unsubstituted hydrocarbyl;
T is a bridging group; and
each of X 1 and X 2 is independently a univalent anionic ligand, or X 1 and X 2 are joined and together with M to form a metallocyclic ring; and
a hafnium metallocene catalyst that is bis(1,5,6-trimethylindenyl) hafnium dichloride.
2. The catalyst system of claim 1 , wherein at least two of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are, independently —R 13 —SiR′ 3 or —R 13 —CR′ 3 wherein R 13 is C 1 to C 4 hydrocarbyl, and each R′ is independently hydrogen or C 1 to C 20 substituted or unsubstituted hydrocarbyl.
3. The catalyst system of claim 1 , wherein R 2 and R 7 are independently —R 13 —SiR′ 3 or —R 13 —CR′ 3 wherein R 13 is a C 1 to C 4 hydrocarbyl and each R′ is independently hydrogen or a C 1 to C 20 substituted or unsubstituted hydrocarbyl.
4. The catalyst system of claim 1 , wherein R 2 and R 7 are independently selected from —CH 2 —SiMe 3 , —CH 2 —SiEt 3 , —CH 2 —SiPr 3 , —CH 2 —SiBu 3 , —CH 2 —SiCy 3 , —CH 2 —C(CH 3 ) 3 , —CH 2 —CH(CH 3 ) 2 , —CH 2 CPh 3 , —CH 2 (C 6 Me 5 ), —CH 2 —C(CH 3 ) 2 Ph, —CH 2 —C(Cy)Ph 2 , —CH 2 —SiH(CH 3 ) 2 , —CH 2 SiPh 3 , —CH 2 —Si(CH 3 ) 2 Ph, —CH 2 —Si(CH 3 )Ph 2 , —CH 2 —Si(Et) 2 Ph, —CH 2 —Si(Et)Ph 2 , —CH 2 —Si(CH 2 ) 3 Ph, —CH 2 —Si(CH 2 ) 4 Ph —CH 2 —Si(Cy)Ph 2 , or —CH 2 —Si(Cy) 2 Ph.
5. The catalyst system of claim 4 , wherein R 2 and R 7 are each —CH 2 —SiMe 3 .
6. The catalyst system of claim 1 , wherein T is selected from is selected from R* 2 C, R* 2 Si, R* 2 CSiR* 2 , R* 2 SiSiR* 2 , R* 2 CSiR* 2 CR* 2 , R* 2 SiCR* 2 SiR* 2 , wherein R* is independently hydrogen or a substituted or unsubstituted C 1 -C 20 hydrocarbyl, or two or more adjacent R* are joined to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent.
7. The catalyst system of claim 2 , wherein T is selected from CH 2 , CH 2 CH 2 , SiMe 2 , SiPh 2 , Si(Me) 2 Si(Me) 2 , SiMePh, or Si(CH 2 ) 3 .
8. The catalyst system of claim 4 , wherein T is R* 2 SiSiR* 2 , wherein each R* is unsubstituted C 1 -C 20 hydrocarbyl.
9. The catalyst system of claim 1 , wherein the catalyst represented by formula (I) is selected from: rac/meso-Me 4 Si 2 (3-Me 3 Si—CH 2 -Cp) 2 HfMe 2 ; rac-Me 4 Si 2 (3-Me 3 Si—CH 2 -Cp) 2 HfMe 2 ; meso-Me 4 Si 2 (3-Me 3 Si—CH 2 -Cp) 2 HfMe 2 ; rac/meso-Me 2 Si(3-Me 3 Si—CH 2 -Cp) 2 HfMe 2 ; rac-Me 2 Si(3-Me 3 Si—CH 2 -Cp) 2 HfMe 2 ; Me 4 Si 2 (Me 4 Cp)(3-Me 3 Si—CH 2 -Cp)HfMe 2 ; Me 2 Si(Me 4 Cp)(3-Me 3 Si—CH 2 -Cp)HfMe 2 ; SiMe 2 (EtMe 3 Cp)(3-CH 2 —SiMe 3 -Cp)HfMe 2 ; SiMe 2 (Me 4 Cp)(3-CH 2 —SiPhMe 2 -Cp)HfMe 2 ; Si 2 Me 4 (Me 4 Cp)(3-CH 2 —SiPhMe 2 -Cp)HfMe 2 ; SiMe 2 (EtMe 3 Cp)(3-CH 2 —SiPh 3 -Cp)HfMe 2 ; Si 2 Me 4 (EtMe 3 Cp)(3-CH 2 —SiPh 3 -Cp)HfMe 2 ; SiMe 2 (Me 4 Cp)(3-CH 2 —SiPh 3 -Cp)HfMe 2 ; SiMe 2 (EtMe 3 Cp)(3-CH 2 —SiPh 3 -Cp)HfMe 2 ; SiMe 2 (2-Me,3-CH 2 —SiMe 3 -Ind) 2 HfMe 2 ; Si 2 Me 4 (2-Me,3-CH 2 —SiMe 3 -Ind) 2 HfMe 2 ; SiMe 2 (2-Me,3-CH 2 —SiPhMe 2 -Ind) 2 HfMe 2 ; Si 2 Me 4 (2-Me,3-CH 2 —SiPhMe 2 -Ind) 2 HfMe 2 ; SiMe 2 (2-Me,3-CH 2 —SiPh 3 -Ind) 2 HfMe 2 ; or Si 2 Me 4 (2-Me,3-CH 2 —SiPh 3 -Ind) 2 HfMe 2 .
10. The catalyst system of claim 1 , wherein the activator is an alkylalumoxane.
11. The catalyst system of claim 1 , wherein the support material is selected from Al 2 O 3 , ZrO 2 , SiO 2 , or SiO 2 /Al 2 O 3 .
12. The catalyst system of claim 1 , wherein the support material is fluorided silica.
13. A process for polymerization of olefin monomers comprising contacting one or more monomers with a catalyst system of claim 1 ; and obtaining a polyolefin.
14. The process of claim 13 , wherein:
contacting comprises contacting in a single reaction zone, in the gas phase or slurry phase, ethylene and C 3 to C 20 comonomer with the catalyst system; and
obtaining a polyolefin comprises obtaining an ethylene polymer having an weight average molecular weight Mw value of 150,000 g/mol or greater and an internal unsaturation content of 0.2 or greater internal unsaturations per 1,000 carbons.
15. The process of claim 14 , wherein the polyolefin has an internal unsaturation content of 0.4 or greater internal unsaturations per 1,000 carbons.
16. The process of claim 14 , wherein the polyolefin has a density of from 0.900 g/cm 3 to 0.95 g/cm 3 .
17. A process for polymerization of olefin monomers comprising contacting in a single reaction zone, in the gas phase or slurry phase, ethylene and C 3 to C 20 comonomer with the catalyst system of claim 2 ; and obtaining an ethylene polymer having an weight average molecular weight Mw value of 150,000 g/mol or greater and an internal unsaturation content of 0.2 or greater internal unsaturations per 1,000 carbons.
18. A process for polymerization of olefin monomers comprising contacting in a single reaction zone, in the gas phase or slurry phase, ethylene and C 3 to C 20 comonomer with the catalyst system of claim 4 ; and obtaining an ethylene polymer having an weight average molecular weight Mw value of 150,000 g/mol or greater and an internal unsaturation content of 0.2 or greater internal unsaturations per 1,000 carbons.
19. A process for polymerization of olefin monomers comprising contacting in a single reaction zone, in the gas phase or slurry phase, ethylene and C 3 to C 20 comonomer with the catalyst system of claim 8 ; and obtaining an ethylene polymer having an weight average molecular weight Mw value of 150,000 g/mol or greater and an internal unsaturation content of 0.2 or greater internal unsaturations per 1,000 carbons.
20. A process for polymerization of olefin monomers comprising contacting in a single reaction zone, in the gas phase or slurry phase, ethylene and C 3 to C 20 comonomer with the catalyst system of claim 9 ; and obtaining an ethylene polymer having an weight average molecular weight Mw value of 150,000 g/mol or greater and an internal unsaturation content of 0.2 or greater internal unsaturations per 1,000 carbons.