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EP-4735458-A1 - METHODS FOR PREPARING METALLOCENE COMPOUNDS

EP4735458A1EP 4735458 A1EP4735458 A1EP 4735458A1EP-4735458-A1

Abstract

Disclosed herein are synthetic methods for improving the solubility of metallocenes such as those that contain perfluorobenzyl(indene) groups. These methods can include alkylation of the perfluoroaryl ring of metallocene precursors using alkyl lithium reagents in a one-pot reaction. Further, these methods can be employed without altering the equipment or conditions of the reaction, without isolation of new intermediates, and while generally retaining desired catalyst characteristics.

Inventors

  • LIEF, GRAHAM R.
  • YANG, QING
  • HASCHKE, ERIC J.

Assignees

  • Chevron Phillips Chemical Company LP

Dates

Publication Date
20260506
Application Date
20240624

Claims (20)

  1. CLAIMS We claim: 1. A metallocene compound having formula (I): ; wherein: M is Zr, Ti, or Hf; X 1 and X 2 independently are a monoanionic ligand; Cp A is a cyclopentadienyl, indenyl, or fluorenyl group with substituent –(CH2)nArR x , and optionally substituted with one or more other substituents; Cp B is a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group; Ar is an aryl group comprising a halogen substituent; R x is a C1 to C18 hydrocarbyl group substituent on Ar; and n is an integer from 0 to 5.
  2. 2. A catalyst composition comprising: (a) metallocene compound having formula (I): ; wherein: M is Zr, Ti, or Hf; X 1 and X 2 independently are a monoanionic ligand; Cp A is a cyclopentadienyl, indenyl, or fluorenyl group with substituent –(CH2)nArR x , and optionally substituted with one or more other substituents; Cp B is a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group; Ar is an aryl group comprising a halogen substituent; R x is a C1 to C18 hydrocarbyl group substituent on Ar; and n is an integer from 0 to 5; (b) an activator comprising an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, a chemically treated solid oxide, or any combination thereof; and (c) optionally, a co-catalyst.
  3. 3. The metallocene compound or catalyst composition of claim 1 or 2, wherein X 1 and X 2 independently are H, F, Cl, Br, or a C 1 to C 12 hydrocarbyl group.
  4. 4. The metallocene compound or catalyst composition of any one of claims 1-3, wherein Ar is a phenyl group with two, three, or four halogen substituents.
  5. 5. The metallocene compound or catalyst composition of any one of claims 1-4, wherein each halogen substituent is F.
  6. 6. The metallocene compound or catalyst composition of any one of claims 1-5, wherein Ar is selected from: R x is selected from methyl, ethyl, n-propyl, n-butyl, sec-butyl, t-butyl, 3-butenyl, n-hexyl, phenyl, and substituted phenyl.
  7. 7. The metallocene compound or catalyst composition of claim 1 or 2, wherein the metallocene compound is selected from: ;
  8. 8. The metallocene compound or catalyst composition of claim 1 or 2, wherein the metallocene compound is: .
  9. 9. The metallocene compound or catalyst composition of any one of claims 1-8, wherein the metallocene compound has a solubility at 25 °C in 1-decene in a range from 0.1 wt. % to 1.0 wt. %.
  10. 10. The metallocene compound or catalyst composition of any one of claims 1-8, wherein the metallocene compound has a solubility at 25 °C in 1-decene in a range from 0.2 wt. % to 0.5 wt. %.
  11. 11. The catalyst composition of any one of claims 2-10, wherein the activator comprises the aluminoxane compound.
  12. 12. The catalyst composition of any one of claims 2-10, wherein the activator comprises the chemically treated solid oxide.
  13. 13. The catalyst composition of claim 12, wherein the chemically treated solid oxide comprises a fluorided solid oxide and/or a sulfated solid oxide.
  14. 14. The catalyst composition of claim 12, wherein the chemically treated solid oxide comprises fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica- zirconia, fluorided silica-titania, fluorided-chlorided silica-coated alumina, fluorided silica- coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or any combination thereof.
  15. 15. The catalyst composition of any one of claims 2-14, wherein the catalyst composition comprises the co-catalyst.
  16. 16. The catalyst composition of claim 15, wherein the co-catalyst comprises trimethylaluminum (TMA), triethylaluminum (TEA), tri-n-propylaluminum (TNPA), tri-n- butylaluminum (TNBA), triisobutylaluminum (TIBA), tri-n-hexylaluminum, tri-n- octylaluminum (TNOA), or any combination thereof.
  17. 17. The catalyst composition of any one of claims 2-16, wherein the catalyst composition further comprises a second metallocene compound.
  18. 18. An oligomerization process comprising contacting the catalyst composition of any one of claims 2-17 with an alpha olefin monomer and optionally H2 under oligomerization conditions to produce an oligomer product.
  19. 19. The oligomerization process of claim 18, wherein: the alpha olefin monomer comprises a C 4 to C 14 alpha olefin or a C 8 to C 12 alpha olefin; the oligomerization process further comprises a step of separating at least a portion of the catalyst composition from the oligomer product; the oligomerization process further comprises a step of separating unreacted alpha olefin monomer from the oligomer product; the oligomerization process further comprises a step of fractionating the oligomer product into an alpha olefin dimer product, an alpha olefin trimer product, and an alpha olefin tetramer and higher oligomer product; the oligomerization process further comprises a step of hydrogenating at least a portion of the oligomer product to form a polyalphaolefin; or any combination thereof.
  20. 20. The oligomerization process of claim 18 or 19, wherein an activity of the catalyst composition in the oligomerization process is within 20%, within 15%, within 10%, or within 5%, of an otherwise identical catalyst composition comprising a metallocene compound in which each R x is F.

Description

METHODS FOR PREPARING METALLOCENE COMPOUNDS REFERENCE TO RELATED APPLICATION [0001] This application is being filed on June 24, 2024, as a PCT International Patent Application and claims the benefit of and priority to U.S. Provisional Patent Application No. 63/510,495, filed on June 27, 2023, the disclosure of which is incorporated herein by reference in its entirety. FIELD OF THE INVENTION [0002] The present disclosure generally relates to methods for preparing metallocene compounds and the use of the metallocene compounds within catalyst compositions for oligomerization and polymerization processes, and more particularly relates to preparing metallocene compounds with improved solubility. BACKGROUND [0003] Metallocene compounds have been developed as effective catalysts for oligomerization and polymerization processes. Structural properties of metallocenes have been finely tuned to produce desired oligomer and polymer characteristics. For example, metallocene compounds comprising at least one indenyl ligand containing at least one halogenated substituent can produce polyethylene having low levels of short chain branching. There is a need for metallocene compounds with improved solubility without altering the properties of the oligomer and polymer produced from a given metallocene compound. Accordingly, it is to this end that the present invention is generally directed. SUMMARY OF THE INVENTION [0004] This summary is provided to introduce a selection of concepts in a simplified form that are further described below in the detailed description. This summary is not intended to identify required or essential features of the claimed subject matter. Nor is this summary intended to be used to limit the scope of the claimed subject matter. [0005] Methods for the preparation of a metallocene compound are disclosed herein, comprising (i) contacting a first compound having formula CpA–(CH2)n–Ar–X with a Bronsted base to form a deprotonated compound; (ii) contacting the deprotonated compound with a substitution reagent to form a substituted compound having formula CpA–(CH2)n–Ar– Rx; and (iii) contacting the substituted compound with a second compound having formula CpB–M–X3 to form a metallocene compound having formula (I): . In certain aspects, M can be can be a halogen or NRy2; 1 2 X and X each can be a can a cyclopentadienyl, indenyl, or fluorenyl group, optionally substituted with one or more other substituents; CpB can be a substituted or unsubstituted cyclopentadienyl, indenyl, or fluorenyl group; Ar can be an aryl group comprising a halogen substituent; Rx can be a C1 to C18 hydrocarbyl group substituent on Ar (e.g., selected from alkyl or alkenyl or aryl; a phenyl group, a benzyl group, a C1 to C8 alkyl group, or a C3 to C8 alkenyl group); and n can be an integer from 0 to 5. [0006] Metallocene compounds are also disclosed herein and can have formula (I) and substituents generally as referenced above. Metallocene compounds disclosed herein can have an improved solubility, relative to metallocenes without an Rx-substituent. Catalyst compositions are also disclosed herein and can comprise metallocene compounds as described above, an activator, and an optional co-catalyst. In certain aspects, the activator can comprise an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, a chemically treated solid oxide, or any combination thereof. [0007] Oligomerization processes are disclosed herein and can comprise contacting a catalyst composition with an alpha olefin monomer, and optionally H2, under oligomerization conditions to produce an oligomer product. Polymerization processes are disclosed herein and can comprise contacting a catalyst composition with an ethylene monomer and an optional α-olefin comonomer in a polymerization reactor system under polymerization conditions to produce an ethylene polymer. [0008] Both the foregoing summary and the following detailed description provide examples and are explanatory only. Accordingly, the foregoing summary and the following detailed description should not be considered to be restrictive. Further, features or variations may be provided in addition to those set forth herein. For example, certain aspects and embodiments may be directed to various feature combinations and sub-combinations described in the detailed description. DEFINITIONS [0009] To define more clearly the terms used herein, the following definitions are provided. Unless otherwise indicated, the following definitions are applicable to this disclosure. If a term is used in this disclosure but is not specifically defined herein, the definition from the IUPAC Compendium of Chemical Terminology, 2nd Ed (1997), can be applied, as long as that definition does not conflict with any other disclosure or definition applied herein, or render indefinite or non-enabled any claim to which that definition is applied. To the extent that any definition or usage provided by any do