Isotactic propylene homopolymers and copolymers produced with C1 symmetric metallocene catalysts
The present disclosure provides catalyst compounds comprising asymmetric bridged metallocenes containing a ligand having at least one saturated ring, catalyst systems including such compounds, and uses thereof. Catalyst compounds of the present disclosure can include indacenyl-type ligands. In another class of embodiments, the present disclosure is directed to polymerization processes to produce polyolefin polymers from catalyst systems including one or more olefin polymerization catalysts, at least one activator, and an optional support.
1 . A catalyst compound represented by the Formula (I):
wherein:
M is zirconium or hafnium;
T is a bridging group;
each of X 1 and X 2 is a halide or a C 1 -C 5 hydrocarbyl, or X 1 and X 2 are joined to form a metallocycle ring;
R 1 is hydrogen, a halogen, an unsubstituted C 1 -C 40 hydrocarbyl, a C 1 -C 40 substituted hydrocarbyl, an unsubstituted C 4 -C 62 aryl, a substituted C 4 -C 62 aryl, an unsubstituted C 4 -C 62 heteroaryl, a substituted C 4 -C 62 heteroaryl, —NR′ 2 , —SR′, —OR, —SiR′ 3 , —OSiR′ 3 , —PR′ 2 , or —R″—SiR′ 3 , where R″ is C 1 -C 10 alkyl and each R′ is hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl;
R 3 is an unsubstituted C 4 -C 62 cycloalkyl, a substituted C 4 -C 62 cycloalkyl, a substituted C 4 -C 62 aryl, an unsubstituted C 4 -C 62 heteroaryl, or a substituted C 4 -C 62 heteroaryl, such that when R 3 is a substituted C 4 -C 62 aryl, it is substituted with at least one of C 1 -C 40 substituted hydrocarbyl, a heteroatom, or a heteroatom-containing group;
each of R 2 and R 4 is independently hydrogen, a halogen, an unsubstituted C 1 -C 40 hydrocarbyl, a C 1 -C 40 substituted hydrocarbyl, an unsubstituted C 4 -C 62 aryl, a substituted C 4 -C 62 aryl, an unsubstituted C 4 -C 62 heteroaryl, a substituted C 4 -C 62 heteroaryl, —NR′ 2 , —SR′, —OR′, —SiR′ 3 , —OSiR′ 3 , —PR′ 2 , or —R″—SiR′ 3 , wherein R″ is C 1 -C 10 alkyl and each R′ is hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl;
each of R 5 , R 6 , R 7 , and R 8 is independently hydrogen, an unsubstituted C 1 -C 40 hydrocarbyl, or a C 1 -C 40 substituted hydrocarbyl; and
J 1 and J 2 are joined to form a substituted or unsubstituted C 4 -C 62 saturated or unsaturated cyclic or polycyclic ring structure, or a combination thereof, provided that J 1 and J 2 together with the two carbons they are bound to on the indenyl group form at least one saturated ring.
2 . A catalyst compound represented by the Formula (III):
wherein:
M is zirconium or hafnium;
T is a bridging group;
each of X 1 and X 2 is a halide or a C 1 -C 5 hydrocarbyl, or X 1 and X 2 are joined to form a metallocycle ring;
R 1 is hydrogen, a halogen, an unsubstituted C 1 -C 40 hydrocarbyl, a C 1 -C 40 substituted hydrocarbyl, an unsubstituted C 4 -C 62 aryl, a substituted C 4 -C 62 aryl, an unsubstituted C 4 -C 62 heteroaryl, a substituted C 4 -C 62 heteroaryl, —NR′ 2 , —SR′, —OR, —SiR′ 3 , —OSiR′ 3 , —PR′ 2 , or —R″—SiR′ 3 , where R″ is C 1 -C 10 alkyl and each R′ is hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl;
each of R 2 and R 4 is independently hydrogen, a halogen, an unsubstituted C 1 -C 40 hydrocarbyl, a C 1 -C 40 substituted hydrocarbyl, an unsubstituted C 4 -C 62 aryl, a substituted C 4 -C 62 aryl, an unsubstituted C 4 -C 62 heteroaryl, a substituted C 4 -C 62 heteroaryl, —NR′ 2 , —SR′, —OR′, —SiR′ 3 , —OSiR′ 3 , —PR′ 2 , or —R″—SiR′ 3 , wherein R″ is C 1 -C 10 alkyl and each R′ is hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl;
each of R 5 , R 6 , R 7 , and R 8 is independently hydrogen, an unsubstituted C 1 -C 40 hydrocarbyl, a C 1 -C 40 substituted hydrocarbyl;
each of R 9 , R 10 , R 11 , R 12 , and R 13 is independently hydrogen, C 1 -C 40 hydrocarbyl or C 1 -C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or two or more of R 9 , R 10 , R 11 , R 12 , and R 13 are joined together to form a C 4 -C 20 cyclic or polycyclic ring structure;
each of R 14 , R 1 , R 18 , and R 19 is independently hydrogen, a halogen, an unsubstituted C 1 -C 40 hydrocarbyl, a C 1 -C 40 substituted hydrocarbyl, an unsubstituted C 4 -C 62 aryl, a substituted C 4 -C 62 aryl, an unsubstituted C 4 -C 62 heteroaryl, a substituted C 4 -C 62 heteroaryl, —NR′ 2 , —SR′, —OR, —SiR′ 3 , —OSiR′ 3 , —PR′ 2 , or —R″—SiR′ 3 , wherein R″ is C 1 -C 10 alkyl and each R′ is hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl, or two or more of R 14 , R 1 , R 16 , R 7 , R 18 , and R 19 are joined together to form cyclic or polycyclic ring structure, or a combination thereof; and
each of R 16 and R 17 is a halogen, an unsubstituted C 1 -C 40 hydrocarbyl, a C 1 -C 40 substituted hydrocarbyl, an unsubstituted C 4 -C 62 aryl, a substituted C 4 -C 62 aryl, an unsubstituted C 4 -C 62 heteroaryl, a substituted C 4 -C 62 heteroaryl, —NR′ 2 , —SR′, —OR′, —SiR′ 3 , —OSiR′ 3 , —PR′ 2 , or —R″—SiR′ 3 , wherein R″ is C 1 -C 10 alkyl and each R′ is hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl, or two or more of R 14 , R 1 , R 16 , R 7 , R 18 , and R 19 are joined together to form cyclic or polycyclic ring structure, or a combination thereof.
3 . A catalyst compound represented by the Formula (IV):
wherein:
M is zirconium or hafnium;
T is a bridging group;
each of X 1 and X 2 is a halide or a C 1 -C 5 hydrocarbyl, or X 1 and X 2 are joined to form a metallocycle ring;
R 1 is hydrogen, a halogen, an unsubstituted C 1 -C 40 hydrocarbyl, a C 1 -C 40 substituted hydrocarbyl, an unsubstituted C 4 -C 62 aryl, a substituted C 4 -C 62 aryl, an unsubstituted C 4 -C 62 heteroaryl, a substituted C 4 -C 62 heteroaryl, —NR′ 2 , —SR′, —OR′, —SiR′ 3 , —OSiR′ 3 , —PR′ 2 , or —R″—SiR′ 3 , where R″ is C 1 -C 10 alkyl and each R′ is hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl;
each of R 2 and R 4 is independently hydrogen, a halogen, an unsubstituted C 1 -C 40 hydrocarbyl, a C 1 -C 40 substituted hydrocarbyl, an unsubstituted C 4 -C 62 aryl, a substituted C 4 -C 62 aryl, an unsubstituted C 4 -C 62 heteroaryl, a substituted C 4 -C 62 heteroaryl, —NR′ 2 , —SR′, —OR′, —SiR′ 3 , —OSiR′ 3 , —PR′ 2 , or —R″—SiR′ 3 , wherein R″ is C 1 -C 10 alkyl and each R′ is hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl;
each of R 5 , R 6 , R 7 , and R 8 is independently hydrogen, an unsubstituted C 1 -C 40 hydrocarbyl, a C 1 -C 40 substituted hydrocarbyl;
each of R 9 , R 10 , R 11 , R 12 , and R 13 is independently hydrogen, C 1 -C 40 hydrocarbyl or C 1 -C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or two or more of R 9 , R 10 , R 11 , R 12 , and R 13 are joined together to form a C 4 -C 20 cyclic or polycyclic ring structure; and
each of R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 is independently hydrogen, a halogen, an unsubstituted C 1 -C 40 hydrocarbyl, a C 1 -C 40 substituted hydrocarbyl, an unsubstituted C 4 -C 62 aryl, a substituted C 4 -C 62 aryl, an unsubstituted C 4 -C 62 heteroaryl, a substituted C 4 -C 62 heteroaryl, —NR′ 2 , —SR′, —OR, —SiR′ 3 , —OSiR′ 3 , —PR′ 2 , or —R″—SiR′ 3 , wherein R″ is C 1 -C 10 alkyl and each R′ is hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl, or two or more of R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 are joined together to form cyclic or polycyclic ring structure, or a combination thereof.
4 . The catalyst compound of claim 1 , wherein T is represented by the formula:
(R* 2 G) g ,
wherein each G is C, Si, or Ge, g is 1 or 2, and each R* is, independently, hydrogen, halogen, C 1 -C 20 unsubstituted hydrocarbyl, a C 1 -C 20 substituted hydrocarbyl, or the two or more R* may join to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent, or
wherein T is selected from the group consisting of CH 2 , CH 2 CH 2 , C(CH 3 ) 2 , (Ph) 2 C, (p-(Et) 3 SiPh) 2 C, SiMe 2 , SiPh 2 , SiMePh, Si(CH 2 ) 3 , Si(CH 2 ) 4 , and Si(CH 2 ) 4 .
5 . The catalyst compound of claim 1 , wherein each of R 5 , R 6 , R 7 , and R 8 is independently an unsubstituted C 1 -C 6 hydrocarbyl, or a substituted C 1 -C 6 hydrocarbyl.
6 . The catalyst compound of claim 1 , wherein R 1 is hydrogen, a substituted C 1 -C 6 hydrocarbyl, or an unsubstituted C 1 -C 6 hydrocarbyl.
7 . The catalyst compound of claim 1 , wherein each of R 2 and R 4 is independently hydrogen, a substituted C 1 to C 6 hydrocarbyl, or an unsubstituted C 1 to C 6 hydrocarbyl.
8 . The catalyst compound of claim 1 , wherein the catalyst compound is selected from the group consisting of:
9 . A process comprising:
introducing propylene, optionally one or more of a C 2 or C 4 to C 40 olefin monomer, preferably a C 4 to C 20 alpha olefin or a C 4 to C 14 α,ω-olefin or a C 4 to C 8 alpha olefin, and a catalyst system formed from the catalyst compound of any one of claims 1-3 and an activator into a reactor at a reactor pressure of from 0.7 bar to 70 bar and a reactor temperature of from 20° C. to 150° C.; and
obtaining a propylene homopolymer or copolymer.
10 . The process of claim 9 , wherein the propylene homopolymer has a Mw of 50,000 to 500,000 g/mol, and T m of greater than 150° C.
11 . The process of claim 9 , wherein the olefin monomer is 1,4-heptadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, 2-methyl-1,6-heptadiene, 2-methyl-1,7-octadiene, 2-methyl-1,8-nonadiene, 2-methyl-1,9-decadiene, 2-methyl-1,10-undecadiene, 2-methyl-1,11-dodecadiene, 2-methyl-1,12-tridecadiene, or 2-methyl-1,13-tetradecadiene.
12 . The process of claim 9 , wherein the propylene copolymer has a Mw value of 50,000 to 500,000 g/mol, and a T m of greater than 148° C., a T m of from 148° C. to 159° C. and T c of from 112° C. to 125° C., from 0.1 wt % to 50 wt % of one or more of C 2 or C 4 to C 20 olefin comonomer, based on a total amount of propylene copolymer, a g′ vis of about 0.5 to about 0.97, a shear thinning ratio of about 0.007 to about 0.12, a complex viscosity as measured by oscillatory shear at a radial frequency of 100 rad/s of about 240 Pa·s to about 1,400 Pa·s, a complex viscosity as measured by oscillatory shear at a radial frequency of 0.1 rad/s of about 2,000 Pa·s to about 60,000 Pa·s, a strain hardening ratio of about 5 to about 25, as determined by dividing a Hencky strain rate at 1.0 sec −1 and 2.5 seconds by a Hencky strain rate at 0.1 sec −1 at 2.5 seconds, at Hencky strain of 2.5 and at Hencky strain rate of 1.0 s −1 , an extensional viscosity of about 600 kPa·s or less, measured at 190° C., and a 1% Secant flexural modulus of about 1,300 MPa to about 2,300 MPa.
13 . The catalyst compound of claim 1 wherein R 3 is selected from cyclohexyl, cyclopentyl, cyclooctyl, adamantyl, benzyl, carbazolyl, and fluorenyl.
14 . The catalyst compound of claim 1 wherein R 3 is a substituted aryl group represented by the formula:
wherein each of R 9 , R 10 , R 11 , R 12 , and R 13 is independently hydrogen, C 1 -C 40 hydrocarbyl or C 1 -C 40 substituted hydrocarbyl, a heteroatom or a heteroatom-containing group, or two or more of R 9 , R 10 , R 11 , R 12 , and R 13 are joined together to form a C 4 -C 20 cyclic or polycyclic ring structure, and at least one of R 9 , R 10 , R 11 , R 12 , and R 13 is a C 1 -C 40 substituted hydrocarbyl, a heteroatom, or a heteroatom-containing group.
15 . The catalyst compound of claim 14 wherein the heteroatom or heteroatom-containing group is independently halogen, —NR′ 2 , —SR′, —OR, —SiR′ 3 , —OSiR′ 3 , —PR′ 2 , or —R″—SiR′ 3 , where R″ is C 1 -C 10 alkyl and each R′ is hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl.
16 . The catalyst compound of claim 1 wherein R 3 is a substituted C 4 -C 62 aryl wherein at least one hydrogen atom of the C 4 -C 62 aryl has been substituted with a group selected from halocarbyl, —OR′, —NR′ 2 , —SR′, —SiR 3 , —OSiR′ 3 , —PR′ 2 , or —R″—SiR′ 3 , wherein R″ is C 1 -C 10 alkyl and each R′ is hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl.
17 . The catalyst compound of claim 2 , wherein T is represented by the formula:
(R* 2 G) g ,
wherein each G is C, Si, or Ge, g is 1 or 2, and each R* is, independently, hydrogen, halogen, C 1 -C 20 unsubstituted hydrocarbyl, a C 1 -C 20 substituted hydrocarbyl, or the two or more R* may join to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent, or
wherein T is selected from the group consisting of CH 2 , CH 2 CH 2 , C(CH 3 ) 2 , (Ph) 2 C, (p-(Et) 3 SiPh) 2 C, SiMe 2 , SiPh 2 , SiMePh, Si(CH 2 ) 3 , Si(CH 2 ) 4 , and Si(CH 2 ) 4 .
18 . The catalyst compound of claim 2 , wherein each of R 5 , R 6 , R 7 , and R 8 is independently an unsubstituted C 1 -C 6 hydrocarbyl, or a substituted C 1 -C 6 hydrocarbyl.
19 . The catalyst compound of claim 2 , wherein R 1 is hydrogen, a substituted C 1 -C 6 hydrocarbyl, or an unsubstituted C 1 -C 6 hydrocarbyl.
20 . The catalyst compound of claim 2 , wherein each of R 2 and R 4 is independently hydrogen, a substituted C 1 to C 6 hydrocarbyl, or an unsubstituted C 1 to C 6 hydrocarbyl.
21 . The catalyst compound of claim 2 , wherein at least one of R 9 , R 10 , R 11 , R 12 , and R 13 is selected from halocarbyl, —OR′, —NR′ 2 , —SR′, —SiR′ 3 , —OSiR′ 3 , —PR′ 2 , or —R″—SiR′ 3 , wherein R″ is C 1 -C 10 alkyl and each R′ is hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl.
22 . The catalyst compound of claim 2 , wherein the catalyst compound is represented by the following chemical formula:
23 . The catalyst compound of claim 3 , wherein T is represented by the formula:
(R* 2 G) g ,
wherein each G is C, Si, or Ge, g is 1 or 2, and each R* is, independently, hydrogen, halogen, C 1 -C 20 unsubstituted hydrocarbyl, a C 1 -C 20 substituted hydrocarbyl, or the two or more R* may join to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent, or
wherein T is selected from the group consisting of CH 2 , CH 2 CH 2 , C(CH 3 ) 2 , (Ph) 2 C, (p-(Et) 3 SiPh) 2 C, SiMe 2 , SiPh 2 , SiMePh, Si(CH 2 ) 3 , Si(CH 2 ) 4 , and Si(CH 2 ) 4 .
24 . The catalyst compound of claim 3 , wherein each of R 5 , R 6 , R 7 , and R 8 is independently an unsubstituted C 1 -C 6 hydrocarbyl, or a substituted C 1 -C 6 hydrocarbyl.
25 . The catalyst compound of claim 3 , wherein R 1 is hydrogen, a substituted C 1 -C 6 hydrocarbyl, or an unsubstituted C 1 -C 6 hydrocarbyl.
26 . The catalyst compound of claim 3 , wherein each of R 2 and R 4 is independently hydrogen, a substituted C 1 to C 6 hydrocarbyl, or an unsubstituted C 1 to C 6 hydrocarbyl.
27 . The catalyst compound of claim 3 , wherein at least one of R 9 , R 10 , R 11 , R 12 , and R 13 is selected from halocarbyl, —OR′, —NR′ 2 , —SR′, —SiR′ 3 , —OSiR′ 3 , —PR′ 2 , or —R″—SiR′ 3 , wherein R″ is C 1 -C 10 alkyl and each R′ is hydrogen, halogen, C 1 -C 10 alkyl, or C 6 -C 10 aryl.
28 . The catalyst compound of claim 3 , wherein the catalyst compound is represented by the following chemical formula: