Metallocene compounds
A metallocene compound of formula (I) wherein: M is an atom of a transition metal; X, same or different, is a hydrogen atom, a halogen atom, or a R, OR, OSO 2 CF 3 , OCOR, SR, NR 2 or PR 2 group, wherein R is C 1 -C 40 hydrocarbon group; L is a divalent bridging group; R 1 , is a C 1 -C 40 hydrocarbon group; R 3 is a C 1 -C 40 hydrocarbon group; R 2 , R 4 , R 5 , R 6 , R 7 and R 8 , equal to or different from each other, are hydrogen atoms or C 1 -C 40 hydrocarbon groups.
1. A metallocene compound of formula (IV):
wherein:
M is a transition metal selected from group 3, 4, 5, 6 or a lanthanide or an actinide group in the Periodic Table of Elements;
p is an integer from 0 to 3, wherein p is equal to a formal oxidation state of M minus 2;
X, is the same or different, and is hydrogen, a halogen, R, OR, OSO 2 CF 3 , OCOR, SR, NR 2 or PR 2 , wherein R is a C 1 -C 40 hydrocarbon group optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements; or two X can optionally form a substituted or unsubstituted butadienyl radical, or a OR′O group, wherein R′ is a divalent radical selected from a C 1 -C 40 alkylidene radical, a C 6 -C 40 arylidene radical, a C 7 -C 40 alkylarylidene radical or a C 7 -C 40 arylalkylidene radical;
L is a divalent bridging group selected from a C 1 -C 20 alkylidene radical, a C 3 -C 20 cycloalkylidene radical, a C 6 -C 20 arylidene radical, a C 7 -C 20 alkylarylidene radical, or a C 7 -C 20 arylalkylidene radical optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements, or a silylidene radical comprising up to 5 silicon atoms;
R 1 is a C 1 -C 40 hydrocarbon group optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
R 3 is a C 1 -C 40 hydrocarbon group optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
R 2 , R 4 and R 5 , are the same or different from each other, and are hydrogen or C 1 -C 40 hydrocarbon groups optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements, with the proviso that at least one among R 2 , R 4 and R 5 is hydrogen;
R 6 and R 7 , are the same or different from each other, and are hydrogen or C 1 -C 40 hydrocarbon groups optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
R 15 and R 16 , are the same or different from each other, and are hydrogen or C 1 -C 40 hydrocarbon groups optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements; and
R 3 with R 4 and/or R 4 with R 5 can optionally join to form a aliphatic or aromatic 3-7 membered ring optionally comprising at least one heteroatom belonging to groups 13-16 of the Periodic Table of Elements, the aliphatic or aromatic 3-7 membered ring optionally can comprise one or more hydrocarbon substituents comprising from 1 to 20 carbon atoms.
2. The metallocene compound of claim 1 , wherein:
M is titanium, zirconium or hafnium;
p is 2;
X is hydrogen, a halogen, or R;
R is a linear or branched, cyclic or acyclic C 1 -C 40 -alkyl radical, C 2 -C 40 alkenyl radical, C 2 -C 40 alkynyl radical, C 6 -C 40 -aryl radical, C 7 -C 40 -alkylaryl radical or C 7 -C 40 -arylalkyl radical, optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
L is Z(R″) 2 , wherein Z is a carbon or a silicon atom, and R″ is a linear or branched, cyclic or acyclic C 1 -C 10 -alkyl radical, C 2 -C 10 alkenyl radical, C 2 -C 10 alkynyl radical, C 6 -C 10 -aryl radical, C 7 -C 10 -alkylaryl radical, or C 7 -C 10 -arylalkyl radical optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements.
3. The metallocene compound of claim 1 , wherein:
R 1 is a linear or branched C 1 -C 20 -alkyl radical;
R 3 is a linear or branched C 1 -C 20 -alkyl radical or a C 6 -C 40 -aryl, radical;
R 2 , R 4 and R 5 are hydrogen; and
R 6 and R 7 are hydrogen or a linear or branched C 1 -C 20 -alkyl radical.
4. The metallocene compound according to claim 1 , wherein R 15 and R 16 are linear or branched C 1 -C 40 -alkyl radicals optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements.
5. A process for preparing a metallocene compound of formula (IV):
wherein:
M is a transition metal selected from group 3, 4, 5, 6 or a lanthanide or an actinide group in the Periodic Table of Elements;
p is an integer from 0 to 3, wherein p is equal to a formal oxidation state of M minus 2;
X, is the same or different, and is hydrogen, a halogen, R, OR, OSO 2 CF 3 , OCOR, SR, NR 2 or PR 2 , wherein R is a C 1 -C 40 hydrocarbon group optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements; or two X can optionally form a substituted or unsubstituted butadienyl radical, or a OR′O group, wherein R′ is a divalent radical selected from a C 1 -C 40 alkylidene radical, a C 6 -C 40 arylidene radical, a C 7 -C 40 alkylarylidene radical or a C 7 -C 40 arylalkylidene radical;
L is a divalent bridging group selected from a C 1 -C 20 alkylidene radical, a C 3 -C 20 cycloalkylidene radical, a C 6 -C 20 arylidene radical, a C 7 -C 20 alkylarylidene radical, or a C 7 -C 20 arylalkylidene radical optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements, or a silylidene radical comprising up to 5 silicon atoms;
R 1 is a C 1 -C 40 hydrocarbon group optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
R 3 is a C 1 -C 40 hydrocarbon group optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
R 2 , R 4 and R 5 , are the same or different from each other, and are hydrogen or C 1 -C 40 hydrocarbon groups optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements, with the proviso that at least one among R 2 , R 4 and R 5 is hydrogen;
R 6 is hydrogen or C 1 -C 40 hydrocarbon groups optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
R 7 is hydrogen;
R 15 and R 16 , are the same or different from each other, and are hydrogen or C 1 -C 40 hydrocarbon groups optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements; and
R 3 with R 4 and/or R 4 with R 5 can optionally join to form a aliphatic or aromatic 3-7 membered ring optionally comprising at least one heteroatom belonging to groups 13-16 of the Periodic Table of Elements, the aliphatic or aromatic 3-7 membered ring optionally can comprise one or more hydrocarbon substituents comprising from 1 to 20 carbon atoms;
the process comprising:
contacting a compound of formula (IVa)
and/or its double bond isomers with a base selected from T j B, TMgT 1 , sodium hydride, potassium hydride, metallic sodium, metallic potassium, or combinations thereof to form a metallocene compound product, wherein:
L is a divalent bridging group selected from a C 1 -C 20 alkylidene radical, a C 3 -C 20 cycloalkylidene radical, a C 6 -C 20 arylidene radical, a C 7 -C 20 alkylarylidene radical, or a C 7 -C 20 arylalkylidene radical optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements, or a silylidene radical comprising up to 5 silicon atoms;
R 1 is a C 1 -C 40 hydrocarbon group optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
R 3 is a C 1 -C 40 hydrocarbon group optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
R 2 , R 4 and R 5 , are the same or different from each other, and are hydrogen or C 1 -C 40 hydrocarbon groups optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements, with the proviso that at least one among R 2 , R 4 and R 5 is hydrogen;
R 6 and R 7 , are the same or different from each other, and are hydrogen or C 1 -C 40 hydrocarbon groups optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
R 15 and R 16 , are the same or different from each other, and are hydrogen or C 1 -C 40 hydrocarbon groups optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements; and
R 3 with R 4 and/or R 4 with R 5 can optionally join to form a aliphatic or aromatic 3-7 membered ring optionally comprising at least one heteroatom belonging to groups 13-16 of the Periodic Table of Elements, the aliphatic or aromatic 3-7 membered ring optionally can comprise one or more hydrocarbon substituents comprising from 1 to 20 carbon atoms
B is an alkali or alkaline earth metal;
j is 1 or 2, wherein j is equal to 1 when B is an alkaline metal, and j is equal to 2 when B is an alkali-earth metal;
T is a linear or branched, cyclic or acyclic C 1 -C 20 -alkyl radical, C 6 -C 20 -aryl radical, C 7 -C 20 -alkylaryl radical, or C 7 -C 20 -arylalkyl radical, optionally comprising one or more Si or Ge atoms;
T 1 is a halogen or OR′″, wherein R′″ is a linear or branched, cyclic or acyclic C 1 -C 40 -alkyl radical, C 6 -C 40 -aryl radical, C 7 -C 40 -alkylaryl radical or C 7 -C 40 -arylalkyl radical, optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements, wherein a molar ratio between the base and a ligand of the formula (IVa) is at least 2:1; and
contacting the metallocene compound product with a compound of formula MX p+2 , wherein:
M is a transition metal selected from group 3, 4, 5, 6 or a lanthanide or an actinide group in the Periodic Table of Elements;
p is an integer from 0 to 3, wherein p is equal to a formal oxidation state of M minus 2; and
X, is the same or different, and is hydrogen, a halogen, R, OR, OSO 2 CF 3 , OCOR, SR, NR 2 or PR 2 , wherein R is a C 1 -C 40 hydrocarbon group optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements; or two X can optionally form a substituted or unsubstituted butadienyl radical, or a OR′O group, wherein R′ is a divalent radical selected from a C 1 -C 40 alkylidene radical, a C 6 -C 40 arylidene radical, a C 7 -C 40 alkylarylidene radical or a C 7 -C 40 arylalkylidene radical.
6. The process for preparing the metallocene compound of claim 5 , wherein B is lithium.
7. The process for preparing the metallocene compound of claim 5 , wherein T is a methyl radical or butyl radical.
8. A ligand of formula (IVa) and its double bonds isomers
wherein:
L is a divalent bridging group selected from a C 1 -C 20 alkylidene radical, a C 3 -C 20 cycloalkylidene radical, a C 6 -C 20 arylidene radical, a C 7 -C 20 alkylarylidene radical, or a C 7 -C 20 arylalkylidene radical optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements, or a silylidene radical comprising up to 5 silicon atoms;
R 1 is a C 1 -C 40 hydrocarbon group optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
R 3 is a C 1 -C 40 hydrocarbon group optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
R 2 , R 4 and R 5 , are the same or different from each other, and are hydrogen or C 1 -C 40 hydrocarbon groups optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements, with the proviso that at least one among R 2 , R 4 and R 5 is hydrogen;
R 6 is hydrogen or C 1 -C 40 hydrocarbon groups optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
R 3 with R 4 and/or R 4 with R 5 can optionally join to form a aliphatic or aromatic 3-7 membered ring optionally comprising at least one heteroatom belonging to groups 13-16 of the Periodic Table of Elements, the aliphatic or aromatic 3-7 membered ring optionally can comprise one or more hydrocarbon substituents comprising from 1 to 20 carbon atoms; and
R 15 and R 16 , are the same or different from each other, and are hydrogen or C 1 -C 40 hydrocarbon groups optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements.
9. The ligand of claim 8 , wherein:
L is Z(R″) 2 , wherein Z is a carbon or a silicon atom, and R″ is a linear or branched, cyclic or acyclic C 1 -C 10 -alkyl radical, C 2 -C 10 alkenyl radical, C 2 -C 10 alkynyl radical, C 6 -C 10 -aryl radical, C 7 -C 10 -alkylaryl radical, or C 7 -C 10 -arylalkyl radical optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements.
10. The ligand of claim 8 , wherein:
R 1 is a linear or branched C 1 -C 20 -alkyl radical;
R 3 is a linear or branched C 1 -C 20 -alkyl radical or a C 6 -C 40 -aryl, radical;
R 2 , R 4 and R 5 are hydrogen; and
R 6 is hydrogen or a linear or branched C 1 -C 20 -alkyl radical.
11. A catalyst system obtained by contacting:
a) at least one metallocene compound of formula (IV)
wherein:
M is a transition metal selected from group 3, 4, 5, 6 or a lanthanide or an actinide group in the Periodic Table of Elements;
p is an integer from 0 to 3, wherein p is equal to a formal oxidation state of M minus 2;
X, is the same or different, and is hydrogen, a halogen, R, OR, OSO 2 CF 3 , OCOR, SR, NR 2 or PR 2 , wherein R is a C 1 -C 40 , hydrocarbon group optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements; or two X can optionally form a substituted or unsubstituted butadienyl radical, or a OR′O group, wherein R′ is a divalent radical selected from a C 1 -C 40 alkylidene radical, a C 6 -C 40 arylidene radical, a C 7 -C 40 alkylarylidene radical or a C 7 -C 40 arylalkylidene radical;
L is a divalent bridging group selected from a C 1 -C 20 alkylidene radical, a C 3 -C 20 cycloalkylidene radical, a C 6 -C 20 arylidene radical, a C 7 -C 20 alkylarylidene radical, or a C 7 -C 20 arylalkylidene radical optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements, or a silylidene radical comprising up to 5 silicon atoms;
R 1 is a C 1 -C 40 hydrocarbon group optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
R 3 is a C 1 -C 40 hydrocarbon group optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
R 2 , R 4 and R 5 , are the same or different from each other, and are hydrogen or C 1 -C 40 hydrocarbon groups optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements, with the proviso that at least one among R 2 , R 4 and R 5 is hydrogen;
R 6 and R 7 , are the same or different from each other, and are hydrogen or C 1 -C 40 hydrocarbon groups optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
R 15 and R 16 , are the same or different from each other, and are hydrogen or C 1 -C 40 hydrocarbon groups optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements; and
R 3 with R 4 and/or R 4 with R 5 can optionally join to form a aliphatic or aromatic 3-7 membered ring optionally comprising at least one heteroatom belonging to groups 13-16 of the Periodic Table of Elements, the aliphatic or aromatic 3-7 membered ring optionally can comprise one or more hydrocarbon substituents comprising from 1 to 20 carbon atoms;
b) at least one alumoxane, or a compound able to form an alkylmetallocene cation; and
c) optionally an organo aluminium compound.
12. A process for (co)polymerizing olefins comprising from 2 to 20 carbon atoms comprising contacting one or more of the olefins under polymerization conditions with the catalyst system of claim 11 .
13. The process according to claim 12 , wherein the olefins are alpha-olefins comprising from 2 to 20 carbon atoms.
14. The process according to claim 12 , wherein the olefins are selected from propylene, ethylene, 1-butene, or combinations thereof.