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BR-112021021366-B1 - POLYMERIZATION PROCESS

BR112021021366B1BR 112021021366 B1BR112021021366 B1BR 112021021366B1BR-112021021366-B1

Abstract

POLYMERIZATION PROCESS. This refers to the polymerization of polyolefins and the synthesis of activators. Polymerization processes involve the polymerization of one or more (C2-C12)α-olefin monomers in the presence of at least one catalyst and at least one cocatalyst to produce a polyolefin. The cocatalyst includes a cation and an anion, wherein the anion has a structure that has a vinyl-terminated alkene, one or more boron atoms, and at least four halogen atoms. The cocatalyst anion is incorporated into a polymer chain of the polyolefin.

Inventors

  • RICHARD J. KEATON
  • JOHN R. STUTZMAN
  • SUSAN O. GUNTHER
  • OLEG V. OZEROV
  • Qingheng Lai
  • Jerzy Klosin
  • MICHAEL J. LESNIAK
  • DAVID M. PEARSON
  • TODD D. SENECAL
  • WILLIAM H.H. WOODWARD
  • Sukrit Mukhopadhyay

Assignees

  • THE TEXAS A&M UNIVERSITY SYSTEM
  • DOW GLOBAL TECHNOLOGIES LLC

Dates

Publication Date
20260310
Application Date
20200430
Priority Date
20190430

Claims (15)

  1. 1. Polymerization process, characterized in that it comprises: polymerizing one or more (C2-C12)α-olefin monomers in the presence of at least one catalyst and at least one cocatalyst to produce a polyolefin; wherein the cocatalyst comprises a cation and an anion, wherein the anion has a structure according to formula (I): and an empirical formula −B11CX11, where R1 is an unsaturated (C2-C20) hydrocarbyl with a vinyl-terminated alkene; each X is independently a halogen atom; and insert the cocatalyst anion into a polyolefin polymer chain.
  2. 2. Process according to claim 1, characterized in that the polyolefin comprises: (1) more than 0 and less than 1 molar percent of the cocatalyst anion, based on the molar composition of the polyolefin, and (2) a density in the range of 0.853 to 0.920 g/cm³.
  3. 3. Process according to claim 1, characterized in that the polyolefin has a dissipation factor lower than that of a corresponding polyolefin composition produced under identical polymeric conditions, except that the molar quantity of the anion of formula (I) is replaced by a comparative anion of formula (Ia):
  4. 4. Polymerization process according to claim 1, characterized in that the polyolefin comprises more than 0 molar percent and less than 1 molar percent of the cocatalyst anion.
  5. 5. Polymerization process according to claim 1, characterized in that R1 has a structure according to formula (III): where n is an integer from 1 to 10.
  6. 6. Polymerization process according to claim 1, characterized in that R1 has a structure according to formula (IV): where y is an integer from 1 to 10, ex is 0, 1, 2, and 3, and where x+y is an integer from 1 to 12.
  7. 7. Polymerization process according to claim 6, characterized in that R1 has a structure according to formula (V): where yex are as defined in claim 6.
  8. 8. Polymerization process according to claim 1, characterized in that the polyolefin has a dissipation factor of less than 0.10 at a frequency of 100 Hz and a temperature of 130 °C or the polyolefin has a dissipation factor of less than 1.00 at a frequency of 10 Hz and a temperature of 130 °C.
  9. 9. Polymerization process according to claim 1, characterized in that the polyolefin has a dissipation factor of less than 10 at a frequency of 1.0 Hz and a temperature of 130 °C or the ethylene-based polymer has a dissipation factor of less than 100 at a frequency of 0.10 Hz and a temperature of 130 °C.
  10. 10. Polymerization process according to claim 1, characterized in that the cocatalyst cation is +N(H)RaN3, wherein each RN is chosen from (C1-C20)alkyl or (C6-C20)aryl.
  11. 11. Polymerization process according to claim 1, characterized in that the cocatalyst cation is +N(H)RN3, wherein at least two RN groups are chosen from (C10-C20)alkyl groups.
  12. 12. Polymerization process according to claim 1, characterized in that the cocatalyst cation is +C(C6H5)3.
  13. 13. Polymerization process according to claim 1, characterized in that the cocatalyst cation is +C(C6H4RC)3, where RC is (C1−C20)alkyl.
  14. 14. Polymerization process according to claim 1, characterized in that the polyolefin is a polyethylene, polyoctene or an ethylene-based copolymer.
  15. 15. Polymerization process according to claim 1, characterized in that each X is a chlorine atom.

Description

CROSS-REFERENCE TO RELATED REQUESTS [001] This application claims priority to provisional patent application No. US 62/840,887, filed April 30, 2019, disclosure of which is incorporated herein in its entirety by reference. TECHNICAL FIELD [002] The embodiments of this disclosure generally relate to alkene-functionalized activators, the synthesis of activators and their polymerization processes of applied olefins. BACKGROUND [003] Olefin-based polymers, such as ethylene-based polymers and propylene-based polymers, are produced via various catalyst systems. The selection of such catalyst systems can be an important factor contributing to the characteristics and properties of olefin-based polymers. Catalyst systems for producing polyethylene-based polymers may include a chromium-based catalyst system, a Ziegler Natta catalyst system, or a molecular catalyst system (either metallocene or non-metallocene). [004] Activators are typically used in conjunction with a metal procatalyst to form an activated catalyst ion pair that is subsequently used in olefin polymerization. As part of the catalyst composition in α-olefin polymerization reactions, the activator may have characteristics that are beneficial for α-olefin polymer production and for final polymer compositions, including the α-olefin polymer. Activator characteristics that enhance α-olefin polymer production include, but are not limited to: rapid procatalyst activation, high catalyst efficiency, high temperature capability, consistent polymer composition, and selective deactivation. [005] As part of the catalyst system, the molecular polymerization procatalyst is activated to generate catalytically active species for polymerization, and this can be achieved by a number of means. One such method employs an activator or cocatalyst that is a Brønsted acid. Brønsted acid salts containing weakly coordinated anions are commonly used to activate molecular polymerization procatalysts, particularly such procatalysts comprising Group IV metal complexes. Brønsted acid salts that are fully ionized are capable of transferring a proton to form a cationic derivative of such Group IV metal complexes. [006] For activators, such as Brønsted acid salts, the cationic component may include cations capable of transferring a hydrogen ion, such as ammonium, sulfonium or phosphonium, for example; or oxidizing cations, such as ferrocenium, silver (I) or lead (II) cations, for example; or highly acidic Lewis cations, such as carbon or silylium, for example. [007] However, since the activator or cocatalyst cations activate the procatalyst, the activators may remain in the polymer composition. As a result, cations and anions can affect the polymer composition. Because not all ions diffuse equally, different ions affect the polymer composition differently. In particular, the ion size, ion charge, ion interaction with the surrounding medium, and ion dissociation energy with available counterions will affect the ion's ability to diffuse through a surrounding medium, such as a solvent, a gel, or a polymeric material. [008] Conventional olefin polymerization activators include weakly coordinated or uncoordinated anions. Weak coordination of the anion has been shown to lead to increased catalytic efficiency of the cationic catalyst. However, since the non-nucleophilic character of the non-coordinating anion also increases diffusion, the residual activating anion in the produced polymer will lower the electrical resistance of the polymer, thereby increasing electrical loss and thus decreasing the insulating capacity of the produced polymer. SUMMARY [009] There are ongoing needs to create activators or cocatalysts that do not diffuse or negatively affect the polymeric properties of the polymer produced, while maintaining the catalytic efficiency of a weakly coordinated anion. Dissemination embodiments include polymerization processes. In one or more embodiments, the polymerization process includes the polymerization of one or more (C2-C12)α-olefin monomers in the presence of at least one catalyst and at least one cocatalyst to produce a polyolefin and then the insertion of the cocatalyst anion into a polymer chain of the polyolefin. The polyolefin comprises (1) more than 0 molar percent and less than 1 molar percent of the cocatalyst anion of the total molar percent of the polyolefin and (2) a density in the range of 0.853 to 0.920 g/cm3. [0010] The cocatalyst includes a cation and an anion. The anion has a structure that includes a vinyl-terminated alkene, one or more boron atoms, and at least four halogen atoms. [0011] In embodiments, the polymerization process involves polymerizing one or more (C2-C12)α-olefin monomers in the presence of at least one catalyst and at least one cocatalyst to produce a polyolefin. The cocatalyst anion is then inserted into a polymer chain of the polyolefin. [0012] The cocatalyst comprises a cation and an anion, the anion has a structure according to formula (