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US-12623997-B2 - Non-coordinating anion activators containing a cation with long chain alkoxy functionalization

US12623997B2US 12623997 B2US12623997 B2US 12623997B2US-12623997-B2

Abstract

Activators may comprise compounds represented by the Formula [Ar(EHR 1 R 2 )(OR 3 )]d+[M k+ Q n ] d , wherein: Ar is an aryl group; E is nitrogen or phosphorous; R 1 is a C 1 -C 30 , optionally substituted, linear alkyl group; R 2 is a C 1 -C 30 , optionally substituted, linear alkyl group; R 3 is a C 10 -C 30 , optionally substituted, linear alkyl group; M is an element selected from group 13 of the Periodic Table of the Elements; d is 1, 2 or 3; k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6; n−k=d; and each Q is independently hydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or halosubstituted-hydrocarbyl radical. Catalysts systems may comprise these activators and methods of preparing polyolefins may use these catalysts systems.

Inventors

  • Catherine A. Faler
  • Margaret T. Whalley

Assignees

  • EXXONMOBIL CHEMICAL PATENTS INC.

Dates

Publication Date
20260512
Application Date
20200804

Claims (19)

  1. 1 . A compound represented by Formula (I): [Ar(EHR 1 R 2 ) (OR 3 )] d + [M k+ Q n ] d− (I) wherein: Ar is a phenyl group; E is nitrogen or phosphorous; R 1 is a C 1 -C 30 , unsubstituted linear alkyl group; R 2 is a C 1 -C 30 , unsubstituted linear alkyl group; R 3 is a C 10 -C 30 , unsubstituted linear alkyl group; M is boron or aluminum; d is 1, 2 or 3; k is 1, 2, or 3; n is 2, 3, 4, 5, or 6; n-k=d; and each Q is a perfluorophenyl, a perchlorophenyl, a perfluoronapthyl, or a perchloronapthyl.
  2. 2 . The compound of claim 1 , wherein R 1 is a C 1 to C 10 linear alkyl group.
  3. 3 . The compound of claim 1 , wherein R 1 is methyl, ethyl, propyl, butyl, pentyl, or hexyl.
  4. 4 . The compound of claim 1 , wherein R 2 is a C 1 -C 20 , optionally substituted, linear alkyl group.
  5. 5 . The compound of claim 1 , wherein R 1 is methyl.
  6. 6 . The compound of claim 1 , wherein R 2 is methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, or n-icosyl.
  7. 7 . The compound of claim 1 , wherein R 3 is n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, or n-icosyl.
  8. 8 . The compound of claim 1 , wherein E is nitrogen.
  9. 9 . The compound of claim 1 , wherein M is boron and k is 3.
  10. 10 . The compound of claim 1 , wherein Q is the perfluorophenyl.
  11. 11 . The compound of claim 1 , wherein R 1 , R 2 , and R 3 together comprise 20 or more carbon atoms.
  12. 12 . The compound of claim 1 , wherein E is phosphorous.
  13. 13 . The compound of claim 1 , wherein the compound has a solubility of at least 10 mM at 25° C. in methylcyclohexane.
  14. 14 . The compound of claim 1 , wherein the compound has a solubility of at least 10 mM at 25° C. in isohexane.
  15. 15 . The compound of claim 1 , wherein the compound has a solubility of at least 10 mM at 25° C. in methylcyclohexane and a solubility of at least 10 mM at 25° C. in isohexane.
  16. 16 . A catalyst system comprising a catalyst and an activator comprising the compound of claim 1 .
  17. 17 . The catalyst system of claim 16 , further comprising a support material.
  18. 18 . A solution comprising the compound of claim 1 and an aliphatic solvent; wherein aromatic solvents are absent.
  19. 19 . A solution comprising the catalyst system of claim 16 and an aliphatic solvent; wherein aromatic solvents are absent.

Description

CROSS-REFERENCE TO RELATED APPLICATION This application is a U.S. national phase application of PCT Application No. PCT/US2020/044865 having a filing date of Aug. 4, 2020, which claims priority to and the benefit of U.S. Provisional Application No. 62/926,956 having a filing date of Oct. 28, 2019, the contents of both are incorporated by reference in their entirety. FIELD This application relates to group 13 metallate activators, catalyst systems comprising the activators, and methods for polymerizing olefins using such activators. BACKGROUND Polyolefins are widely used commercially because of their robust physical properties. Polyolefins are typically prepared with a catalyst that polymerizes olefin monomers. Therefore, there is interest in finding new catalysts and catalyst systems that provide polymers having improved properties. Catalysts for olefin polymerization are often based on metallocenes as catalyst precursors, which are activated either with an alumoxane or an activator containing a non-coordinating anion. A non-coordinating anion, such as tetrakis(pentafluorophenyl)borate, is capable of stabilizing the resulting metal cation of the catalyst. Because such activators are fully ionized and the corresponding anion is highly non-coordinating, such activators can be effective as olefin polymerization catalyst activators. However, because they are ionic salts, such activators are frequently insoluble in aliphatic hydrocarbons and only sparingly soluble in aromatic hydrocarbons. It is desirable to conduct most polymerizations of α-olefins in aliphatic hydrocarbon solvents due to the compatibility of such solvents with the olefin monomer and in order to reduce the aromatic hydrocarbon content of the resulting polymer product. Typically, ionic salt activators are added to such polymerizations in the form of a solution in an aromatic solvent such as toluene. The use of even a small quantity of such an aromatic solvent for this purpose is undesirable since it must be removed in a post-polymerization devolatilization step and separated from other volatile components, which is a process that adds significant cost and complexity to any commercial process. In addition, the activators often exist in the form of an oily, intractable material which is not readily handled and metered or precisely incorporated into the reaction mixture. There is a need for activators that are soluble in aliphatic hydrocarbon solvents and capable of producing polyolefins at high activity levels. In particular, there is a need for activators that may be economically prepared and possessing solubilities eliminating the need to use aromatic solvents in the polymerization process. It is therefore an object of the present invention to provide activators, catalyst systems comprising these activators, and methods for the polymerization of olefins using such activators and catalyst systems. SUMMARY Activators described herein may comprise a compound represented by Formula (I): [Ar(EHR1R2)(OR3)]d+[Mk+Qn]d−  (I) wherein: Ar is an aryl group;E is nitrogen or phosphorous;R1 is a C1-C30, optionally substituted, linear alkyl group;R2 is a C1-C30, optionally substituted, linear alkyl group;R3 is a C10-C30, optionally substituted, linear alkyl group;M is an element selected from group 13 of the Periodic Table of the Elements;d is 1, 2 or 3; k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6; n−k=d; andeach Q is independently hydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or halosubstituted-hydrocarbyl radical. Activators described herein may also comprise a compound represented by Formula (II): [Cat]+[MQ4]−  (II) wherein: M is an element selected from group 13 of the Periodic Table of the Elements;Q is a hydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, or halosubstituted-hydrocarbyl radical; and[Cat]+ is a cation represented by a structure selected from the group consisting of Activators described herein may also comprise a compound represented by Formula (III): [R11R12R13EH]+[BR14R15R16R17]−  (II) wherein: E is nitrogen or phosphorous;each of R11, R12, and R13 is independently a C1-C30 linear alkyl group or an aryl group, wherein the aryl group is substituted with at least one C10-C30 alkoxy group, wherein R11, R12, and R13 together comprise 26 or more carbon atoms; andeach of R14, R15, R16, and R17 is independently an aryl group, wherein at least one of R14, R15, R16, and R17 is substituted with from one to seven fluorine atoms. Catalyst systems described herein may comprise an activator as described herein and a catalyst compound represented by Formula (IV): wherein in Formula (IV): Mc is an element selected from group 4 of the Periodic Table of the Elements;n is 0 or 1;T is an optional bridging group selected from S, O, PR′, NR′, SiR″2, CH2, CHR″, or C