Metallocene compounds

A bridged metallocene compound of formula (Ia):

• wherein
• T1, T2, T3 and T4 are oxygen or sulfur;
• n is 1 or 2;
• M is an atom of a transition metal selected from group 4 or the actinide group in the Periodic Table of Elements;
• L is a divalent bridging group selected from a C1-C20 alkylidene, a C3-C20 cycloalkylidene, a C6-C20 arylidene, a C7-C20 alkylarylidene, or a C7-C20 arylalkylidene, optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements, or L is a silylidene radical comprising up to 5 silicon atoms;
• X, equal to or different from each other, is hydrogen, a halogen, R, OR, OSO2CF3, OCOR, SR, NR2, or PR2, or two X groups can be joined to form OR′O;
• R is a linear or branched, cyclic or acyclic, C1-C40-alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C6-C40-aryl, C7-C40-alkylaryl or C7-C40-arylalkyl, optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
• R′ is a C1-C20-alkylidene, C6-C20-arylidene, C7-C20-alkylarylidene, or C7-C20-arylalkylidene radical;
• W is an aromatic 5 or 6 membered ring optionally comprising at least one heteroatom belonging to groups 15-16 of the Periodic Table of Elements, wherein the valence of each atom of said 5 or 6 membered ring is substituted with hydrogen, or is optionally substituted with at least one R5;
• R5, equal to or different from each other, is a C1-C40 hydrocarbon, optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
• R1 is a linear C1-C40 hydrocarbon, optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
• R4 is hydrogen, or a C1-C40 hydrocarbon optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
• and
• R18, equal to or different from each other, are hydrogen or a C1-C40 hydrocarbon, optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements.

A bridged metallocene compound of formula (Ib):

• wherein
• n is 1 or 2;
• M is an atom of a transition metal selected from group 4 or the actinide group in the Periodic Table of Elements;
• X, equal to or different from each other, is hydrogen, a halogen, R, OR, OSO2CF3, OCOR, SR, NR2, or PR2, or two X groups can be joined to form OR′O;
• R is a linear or branched, cyclic or acyclic, C1-C40-alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C6-C40-aryl, C7-C40-alkylaryl or C7-C40-arylalkyl, optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
• R′ is a C1-C20-alkylidene, C6-C20-arylidene, C7-C20-alkylarylidene, or C7-C20-arylalkylidene radical;
• L is a divalent bridging group selected from a C1-C20 alkylidene, a C3-C20 cycloalkylidene, a C6-C20 arylidene, a C7-C20 alkylarylidene, or a C7-C20 arylalkylidene, optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements, or L is a silylidene radical comprising up to 5 silicon atoms;
• W is an aromatic 5 or 6 membered ring optionally comprising at least one heteroatom belonging to groups 15-16 of the Periodic Table of Elements, wherein the valence of each atom of said 5 or 6 membered ring is substituted with hydrogen, or is optionally substituted with at least one R5;
• R5, equal to or different from each other is a C1-C40 hydrocarbon optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements:
• T1 and T2, equal to or different from each other, are oxygen, sulfur, or C(R18)2, with the proviso that at least one of T1 and T2 is oxygen or sulfur;
• R18, equal to or different from each other, are hydrogen or a C1-C40 hydrocarbon, optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
• R1 is a linear C1-C40 hydrocarbon, optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
• and
• R4 is hydrogen, or a C1-C40 hydrocarbon optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements.

A catalyst system for polymerizing at least one olefin, the catalyst system obtained by contacting:

• a bridged metallocene compound of formula (I)
• wherein:
• M is an atom of a transition metal selected from group 4 or the actinide group in the Periodic Table of Elements;
• X, equal to or different from each other, is hydrogen, a halogen, R, OR, OSO2CF3, OCOR, SR, NR2, or PR2, or two X groups can be joined to form OR′O;
• R is a linear or branched, cyclic or acyclic, C1-C40-alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C6-C40-aryl, C7-C40-alkylaryl or C7-C40-arylalkyl, optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
• R′ is a C1-C20-alkylidene, C6-C20-arylidene, C7-C20-alkylarylidene, or C7-C20-arylalkylidene radical;
• L is a divalent bridging group selected from a C1-C20 alkylidene, a C3-C20 cycloalkylidene, a C6-C20 arylidene, a C7-C20 alkylarylidene, or a C7-C20 arylalkylidene, optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements, or L is a silylidene radical comprising up to 5 silicon atoms;
• R1 is a linear C1-C40 hydrocarbon, optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
• T1 and T2, equal to or different from each other, are oxygen, sulfur, or C(R18)2, with the proviso that at least one of T1 and T2 is oxygen or sulfur;
• R18, equal to or different from each other, are hydrogen or a C1-C40 hydrocarbon, optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
• n is 1, 2 or 3;
• T3 and T4, equal to or different from each other, are oxygen, sulfur, or C(R18)2;
• R4 is hydrogen, or a C1-C40 hydrocarbon optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
• W is an aromatic 5 or 6 membered ring optionally comprising at least one heteroatom belonging to groups 15-16 of the Periodic Table of Elements, wherein the valence of each atom of said 5 or 6 membered ring is substituted with hydrogen, or is optionally substituted with at least one R5;
• and
• R5, equal to or different from each other, is a C1-C40 hydrocarbon, optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
• at least one alumoxane, or a compound capable of forming an alkylmetallocene cation;
• and
• optionally an organo aluminum compound.

A process for preparing an alpha-olefin polymer comprising, contacting under polymerization conditions, at least one alpha-olefin of formula CH2═CHA, wherein A is hydrogen or a C1-C20 alkyl, with a catalyst system comprising:

• a bridged metallocene compound of formula (I)
• wherein:
• M is an atom of a transition metal selected from group 4 or the actinide group in the Periodic Table of Elements;
• X, equal to or different from each other, is hydrogen, a halogen, R, OR, OSO2CF3, OCOR, SR, NR2, or PR2, or two X groups can be joined to form OR′O;
• R is a linear or branched, cyclic or acyclic, C1-C40-alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C6-C40-aryl, C7-C40-alkylaryl or C7-C40-arylalkyl, optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
• R′ is a C1-C20-alkylidene, C6-C20-arylidene, C7-C20-alkylarylidene, or C7-C20-arylalkylidene radical;
• L is a divalent bridging group selected from a C1-C20 alkylidene, a C3-C20 cycloalkylidene, a C6-C20 arylidene, a C7-C20 alkylarylidene, or a C7-C20 arylalkylidene, optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements, or L is a silylidene radical comprising up to 5 silicon atoms;
• R1 is a linear C1-C40 hydrocarbon, optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
• T1 and T2, equal to or different from each other, are oxygen, sulfur, or C(R18)2, with the proviso that at least one of T1 and T2 is oxygen or sulfur;
• R18, equal to or different from each other, are hydrogen or a C1-C40 hydrocarbon, optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
• n is 1, 2 or 3;
• T3 and T4, equal to or different from each other, are oxygen, sulfur, or C(R18)2;
• R4 is hydrogen, or a C1-C40 hydrocarbon optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
• W is an aromatic 5 or 6 membered ring optionally comprising at least one heteroatom belonging to groups 15-16 of the Periodic Table of Elements, wherein the valence of each atom of said 5 or 6 membered ring is substituted with hydrogen, or is optionally substituted with at least one R5;
• and
• R5, equal to or different from each other, is a C1-C40 hydrocarbon, optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
• at least one alumoxane, or a compound capable of forming an alkylmetallocene cation;
• and
• optionally an organo aluminum compound.

A ligand of formula (III)

• and double bond isomers thereof,
• wherein
• n is 1, 2, or 3;
• L is a divalent bridging group selected from a C1-C20 alkylidene, a C3-C20 cycloalkylidene, a C6-C20 arylidene, a C7-C20 alkylarylidene, or a C7-C20 arylalkylidene, optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements, or L is a silylidene radical comprising up to 5 silicon atoms;
• R1 is a linear C1-C40 hydrocarbon, optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
• T1 and T2, equal to or different from each other, are oxygen, sulfur, or C(R18)2, with the proviso that at least one of T1 and T2 is oxygen or sulfur;
• R18, equal to or different from each other, are hydrogen or a C1-C40 hydrocarbon, optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
• T3 and T4, equal to or different from each other, are oxygen, sulfur, or C(R18)2;
• R4 is hydrogen, or a C1-C40 hydrocarbon optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements;
• W is an aromatic 5 or 6 membered ring optionally comprising at least one heteroatom belonging to groups 15-16 of the Periodic Table of Elements, wherein the valence of each atom of said 5 or 6 membered ring is substituted with hydrogen, or is optionally substituted with at least one R5;
• and
• R5, equal to or different from each other, is a C1-C40 hydrocarbon, optionally comprising at least one heteroatom belonging to groups 13-17 of the Periodic Table of Elements.