# US 9,868,797 B2 · Bridged metallocene complex for olefin polymerization > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,868,797 B2 - Document ID: US9868797B2 - Status: Granted - Kind: B2 - Application number: 14/907,923 - Filed: 2014-07-29 - Published: 2016-06-16 - Granted: 2018-01-16 - Earliest claimed: 2013-08-01 - Assignees: Saudi Basic Industries Corporation; Sabic Global Technologies B.V. - Applicants: Saudi Basic Industries Corporation; Sabic Global Technologies B.V. - Inventors: Nedumbamana Sankaran; Prashant Sukumar Shinge; Sharankumar Shetty; Girish Chandra; Haif Al-Shammari; Abdulaziz Hamad Al-Humydi; Edward Joseph Nesakumar - Web page: https://patentgrep.com/patent/US9868797B2 ## CPC - C08F 4/76: selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum - C07C 211/48: N-alkylated amines - C07C 211/52: the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups - C07F 5/02: Boron compounds - C07F 5/025: {Boronic and borinic acid compounds} - C07F 17/00: Metallocenes - C08F 4/6592: containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring - C08F 10/02: Ethene - C07C 2602/08: the other ring being five-membered, e.g. indane - C08F 4/65908: {in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+} - C08F 4/65912: {in combination with an organoaluminium compound} - C08F 4/65916: {supported on a carrier, e.g. silica, MgCl2, polymer} - C08F 2420/02: Cp or analog bridged to a non-Cp X anionic donor - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22) ## Abstract A metallocene complex according to formula 1 wherein M is a metal selected from lanthanides or transition metals from group 3, 4, 5, or 6, Q is an anionic ligand to M, k is the number of Q groups and equals the valence of M minus 2, X is a cyclic bridging group that is bonded to a carbon atom of the cyclopentadienyl ligand and to nitrogen, Z1, and Z4 are hydrogen or a hydrocarbon radical with 1-20 carbon atoms; adjacent substituents Z2 and Z3 and are connected to form an indenyl or tetrahydroindenyl ring system and R is hydrogen or a hydrocarbon radical with 1-20 carbon atoms. Also described is a composition comprising the metallocene complex, a process for the preparation of the complex, and a process for the polymerization of olefin polymers in the presence of the metallocene complex. ## Claims ### Claim 1 A metallocene complex according to formula 1 wherein M is a lanthanide metal or a transition metal of group 3, 4, 5, or 6 of the Periodic System of the Elements; Q is an anionic ligand to M; k is the number of Q groups and equals the valence of M minus 2; X is a cyclic bridging group; Z1 and Z4 are identical or different and are hydrogen or a hydrocarbon radical with 1-20 carbon atoms; adjacent substituents Z2 and Z3 are connected to form a 2-indenyl or 2-tetrahydroindenyl ring system together with the carbon atoms of the Cp ring to which they are bound; and R is hydrogen or a hydrocarbon radical with 1-20 carbon atoms. ### Claim 2 (depends on 1) The metallocene complex according to claim 1, wherein the metal M is Ti, Zr, Hf, V, or Sm, and wherein Q is a halogen or a hydrocarbyl group comprising 1 to 20 carbon atoms. ### Claim 3 (depends on 1) The metallocene complex according to claim 1, wherein X is cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclohexenylene, cyclohexadienylene, tolylene, benzylene, naphthylene, anthrylene, pyrenylene, biphenylene or binaphthylene. ### Claim 4 (depends on 1) The metallocene complex according to claim 1, wherein the metallocene complex comprises a 2-indenyl group and is represented by formula 4 wherein M is Ti, Zr, or Hf; X is a cyclic bridging group; R is hydrogen or a hydrocarbon radical with 1-20 carbon atoms; Q is chlorine or a methyl group; and k is the number of Q groups and equals the valence of M minus 2, wherein k is an integer. ### Claim 5 (depends on 4) The metallocene complex according to claim 4, wherein M is Zr; R is t-butyl; Q is chlorine or methyl; k=2; and X is phenylene, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclohexenylene, cyclohexadienylene, tolylene, benzylene, naphthylene, anthrylene, pyrenylene, biphenylene or binaphthylene. ### Claim 6 (depends on 1) The metallocene complex according to claim 1, wherein the metallocene complex is present on a support. ### Claim 7 A process for the preparation of the metallocene complex according to formula 5 comprising: a) reacting 2-bromophenyl boronic acid with 1,8-diaminonaphthalene to form a protected compound according to formula 13, b) reacting the protected compound (13) with a compound according to formula 14, in the presence of a Pd catalyst and in the presence of a base to form a protected compound according to formula 15, c) deprotecting the protected compound (15) by reaction with an acid to provide the compound according to formula 16, reacting the compound (16) with an N-substituted 2-bromoaniline in the presence of a Pd catalyst and in the presence of a base, to form a ligand precursor according to formula 11, wherein the N-substituted 2-bromoaniline is substituted with hydrogen or a hydrocarbon radical with 1-20 carbon atoms, d) creating an anion of the ligand precursor (11) with an organic or inorganic base, e) reacting the anion of the ligand precursor with (Me2N)aMQk, wherein Me is methyl; M is a lanthanide metal or a transition metal of group 3, 4, 5 or 6 of the Periodic System of the Elements; Q is an anionic ligand to M; k is the number of Q groups and equals the valence of M minus 2; and a equals the valence of M minus k, to yield a metallocene complex according to formula 5. ### Claim 8 (depends on 1) A process for the preparation of an olefin polymer, comprising polymerizing one or more olefins in the presence of the metallocene complex according to claim 1 and a cocatalyst. ### Claim 9 (depends on 8) The process according to claim 8, wherein the olefins comprise a mixture of ethylene and at least one other olefin of 3 or more carbon atoms. ### Claim 10 (depends on 1) The metallocene complex according to claim 1, wherein the metal M is Ti, Zr, or Hf; Q is a halogen or a hydrocarbyl group comprising 1 to 20 carbon atoms, X is cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclohexenylene, cyclohexadienylene, tolylene, benzylene, naphthylene, anthrylene, pyrenylene, biphenylene or binaphthylene. ### Claim 11 (depends on 10) A process for the preparation of an olefin polymer, comprising polymerizing one or more olefins in the presence of the metallocene complex according to claim 10 and an aluminium- or boron-containing cocatalyst. ### Claim 12 (depends on 10) The metallocene complex according to claim 10, wherein X is a 2,2′-biphenylene group. ### Claim 13 (depends on 12) A process for the preparation of an olefin polymer, comprising polymerizing one or more olefins in the presence of the metallocene complex according to claim 12 and an aluminium- or boron-containing cocatalyst. ### Claim 14 (depends on 7) The method of claim 7, wherein the N-substituted 2-bromoaniline is N-tert-butyl-2-bromoaniline; the metal M is Ti, Zr, Hf, V, or Sm; and Q is a halogen or a hydrocarbyl group comprising 1 to 20 carbon atoms. ### Claim 15 (depends on 12) The method of claim 12, wherein the metal M is Zr; Q is chlorine or a methyl; and k=2.