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BR-112024010685-B1 - Sulfated Bentonite Compositions and Metallocene Catalytic Compositions

BR112024010685B1BR 112024010685 B1BR112024010685 B1BR 112024010685B1BR-112024010685-B1

Abstract

MODIFICATIONS OF SULFATED BENTONITES AND THEIR USES IN METALLOCENE CATALYST SYSTEMS FOR OLEFIN POLYMERIZATION. These are sulfated bentonite compositions characterized by a total pore volume of 0.4 to 1 ml/g, a total BET surface area of 200 to 400 m²/g, and an average pore diameter of 55 to 100 Angstroms. Sulfated bentonite compositions can also be characterized by an average d50 particle size in the range of 15 to 50 μm and a d90/d10 ratio of 3 to 15. Sulfated bentonite compositions may contain sulfated bentonite and 10 to 90% by weight of colloidal particles, or sulfated bentonite compositions may contain sulfated bentonite and 0.2 to 10 mmol/g of zinc and/or phosphorus. These compositions can be used in metallocene catalyst systems to produce ethylene-based polymers.

Inventors

  • MAX P. MCDANIEL
  • Qing Yang
  • RYAN N. ROSE
  • KATHY S. CLEAR
  • GRAHAM R. LIEF
  • ERIC D. SCHWERDTFEGER
  • Anand Ramanathan
  • JEREMY M. PRAETORIUS
  • CONNOR D. BOXELL

Assignees

  • CHEVRON PHILLIPS CHEMICAL COMPANY LP

Dates

Publication Date
20260310
Application Date
20221213
Priority Date
20211216

Claims (20)

  1. 1. A composition of sulfated bentonite, characterized by: a total pore volume of 0.4 to 1 ml/g; a total BET surface area of 200 to 400 m2/g; and an average pore diameter of 55 to 100 Angstroms (Ang); and wherein the composition contains 25 to 35% by weight of silicon.
  2. 2. Composition according to claim 1, characterized in that 18 to 95% of the total pore volume is in pores with diameters greater than or equal to 60 Å.
  3. 3. Composition according to claim 1, characterized in that the composition has a pore volume of 0.08 to 0.5 mL/g in pores with diameters greater than or equal to 60 Å.
  4. 4. Composition according to claim 1, characterized in that 7 to 60% of the total BET surface area is in pores with diameters greater than or equal to 60 Ang.
  5. 5. Composition according to claim 1, characterized in that the composition has a surface area of 15 to 150 m2/g in pores with diameters greater than or equal to 60 Å.
  6. 6. Composition according to claim 1, further characterized by: an average particle size d50 of 15 to 50 μm; and a d90/d10 ratio of 3 to 15.
  7. 7. Composition according to claim 1, characterized in that: the total pore volume is 0.45 to 0.8 ml/g; the total BET surface area is 225 to 375 m2/g; and the average pore diameter is 55 to 85 Å.
  8. 8. Composition according to claim 7, characterized in that: 25 to 85% of the total pore volume is in pores with diameters greater than or equal to 60 Ang; and 9 to 53% of the total BET surface area is in pores with diameters greater than or equal to 60 Ang.
  9. 9. Composition according to claim 7, characterized in that the composition has: a pore volume of 0.1 to 0.38 ml/g, in pores with diameters greater than or equal to 60 Å; and/or a surface area of 22 to 120 m²/g, in pores with diameters greater than or equal to 60 Å.
  10. 10. Composition according to claim 1, characterized in that the composition contains: 2 to 7% by weight of calcium; or 0.05 to 0.5% by weight of sodium; or 0.05 to 0.5% by weight of strontium; or 2 to 6% by weight of sulfur; or 0.25 to 1% by weight of titanium; or any combination thereof.
  11. 11. Catalytic composition, characterized in that it comprises: a metallocene compound; a cocatalyst; and the sulfated bentonite composition, as defined in claim 1.
  12. 12. Composition according to claim 11, characterized in that the cocatalyst comprises an organoaluminum compound, an organozinc compound, an aluminoxane compound, an organoboron or organoborate compound, an ionizing ionic compound, or any combination thereof.
  13. 13. Composition according to claim 6, characterized in that the composition has a particle size range of 1 to 3.2.
  14. 14. Composition according to claim 6, characterized in that the composition has a particle size d10 of 4 to 25 μm.
  15. 15. Composition according to claim 6, characterized in that the composition has a d90/d50 ratio of 1.5 to 3.5.
  16. 16. Composition according to claim 11, characterized in that the metallocene compound comprises a bridging metallocene compound.
  17. 17. Composition according to claim 11, characterized in that the metallocene compound comprises an unbridged metallocene compound.
  18. 18. Composition according to claim 11, characterized in that the catalytic composition comprises two or more metallocene compounds.
  19. 19. A composition of sulfated bentonite, characterized in that it comprises: a sulfated bentonite; and from 0.2 to 10 mmol of zinc, phosphorus, or both, per g of sulfated bentonite.
  20. 20. Composition according to claim 19, characterized in that the composition comprises from 0.3 to 8 mmol/g of zinc.

Description

REFERENCE TO RELATED REQUEST [001] This application is being filed on December 13, 2022, as a PCT International Patent Application and claims the benefit and priority to U.S. Provisional Patent Application No. 63/290,088, filed on December 16, 2021, the disclosure of which is incorporated herein by reference in its entirety. FIELD OF THE INVENTION [002] This disclosure relates generally to the modification of sulfated bentonites and, more particularly, to the use of metallocene-based catalyst systems containing modified sulfated bentonite supports in olefin polymerization processes. FUNDAMENTALS OF THE INVENTION [003] There are many activators, such as aluminoxanes, organobores, ionizing ionic compounds, and chemically treated solid oxides, that can be used in metallocene catalyst systems to polymerize olefins and, in particular, ethylene. However, there is a need for additional solid activators that provide acceptable catalytic activity in olefin polymerization processes. Consequently, it is to these purposes that the present invention is generally directed. SUMMARY OF THE INVENTION [004] This summary is provided to present a selection of concepts that are better described below in the detailed description. This summary is not intended to identify necessary or essential features of the claimed subject matter. Nor is it intended to be used to limit the scope of the claimed subject matter. [005] In one aspect, the present invention discloses sulfated bentonite compositions characterized by a total pore volume of 0.4 to 1 ml/g, a total BET surface area of 200 to 400 m2/g, and an average pore diameter of 55 to 100 Ang (Angstroms). In another aspect, the present invention discloses sulfated bentonite compositions characterized by an average particle size d50 in the range of 15 to 50 μm and a d90/d10 ratio of 3 to 15. In yet another aspect, the present invention discloses sulfated bentonite compositions comprising sulfated bentonite and 0.2 to 10 mmol of zinc, phosphorus, or both zinc and phosphorus, per g of sulfated bentonite. In yet another aspect, the present invention discloses a sulfated bentonite composition comprising a sulfated bentonite and 10 to 90% by weight of colloidal particles, based on the sulfated bentonite composition. [006] Catalytic compositions are also provided herein, and such catalytic compositions may comprise a metallocene compound, a cocatalyst, and any of the sulfated bentonite compositions disclosed herein. Polymerization processes using catalytic compositions may comprise contacting the catalytic composition with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer. [007] Ethylene-based polymers produced by polymerization processes may have a Mw in the range of 350 to 700 kg/mol, an Mw/Mn ratio in the range of 2 to 4, an Mz/Mw ratio in the range of 1.8 to 4, a CY-a parameter in the range of 0.4 to 0.65, and (a) in some respects, a relaxation time as a function of Mz that is greater than 9.818x10-7(Mz)2 + 0.001503(Mz) - 0.5, where Mz is in kg/mol and relaxation time is in s, and (b) in other respects, a viscosity at 0.1 s-1 as a function of Mz that is greater than 0.0985(Mz)2 + 890.7(Mz) - 300000, where Mz is in kg/mol and the viscosity is in Pa-s. [008] Both the aforementioned summary and the following detailed description provide examples and are for illustrative purposes only. Consequently, the preceding summary and the following detailed description should not be considered restrictive. Furthermore, features or variations may be provided beyond those set forth in this document. For example, certain aspects and modalities may be directed to various combinations and subcombinations of features described in the detailed description. BRIEF DESCRIPTION OF THE FIGURES [009] Figure 1 presents a graph of catalyst activities versus the heat treatment temperature of sulfated bentonite for Example 1. [010] Figures 2-3 show graphs of catalytic activities versus the weight ratio of metallocene compound to sulfated bentonite for Example 5. [011] Figure 4 presents a graph of the particle size distributions of the sulfated bentonite compositions of Example 38, Example 38B and Example 39. [012] Figure 5 presents a graph of the pore volume distributions as a function of pore diameter (Ang, Angstroms) for the sulfated bentonite compositions of Examples 38-42 (Cat 1-5). [013] Figure 6 presents a graph of the surface area distributions as a function of pore diameter (Ang, Angstroms) for the sulfated bentonite compositions of Examples 38-42 (Cat 1-5). [014] Figure 7 presents a graph of the particle size distributions of the sulfated bentonite compositions of Examples 43-45. [015] Figure 8 presents a graph of relaxation time (s) versus average molecular weight z (kg/mol) for the polymers of Examples 48-49 and comparative polymers. [016] Figure 9 presents a graph of viscosity measured at 0.1 s-1 (Pa-s) versus