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CN-116194491-B - Hydrocarbon-modified methylaluminoxane cocatalyst of diphenyl phenoxy metal-ligand complex

CN116194491BCN 116194491 BCN116194491 BCN 116194491BCN-116194491-B

Abstract

A process for polymerizing olefin monomers. The process comprises reacting ethylene and optionally one or more olefin monomers in the presence of a catalytic system comprising a modified hydrocarbylmethylaluminoxane having less than 50 mole percent of AlR A1 R B1 R C1 , based on total moles of aluminum, wherein R A1 、R B1 and R C1 are independently linear (C 1 -C 40 ) alkyl, branched (C 1 -C 40 ) alkyl, or (C 6 -C 40 ) aryl, and one or more metal-ligand complexes according to formula (I).

Inventors

  • P.P. Fontaine
  • D.M. Pearson
  • H.Q.Du
  • J. E. Droben
  • R China Zijie
  • R.A. BAILEY
  • R .cong

Assignees

  • 陶氏环球技术有限责任公司

Dates

Publication Date
20260508
Application Date
20210205

Claims (17)

  1. 1. A process for polymerizing olefin monomers, the process comprising reacting ethylene and optionally one or more olefin monomers in the presence of a catalyst system, wherein the catalyst system comprises: A hydrocarbyl-modified methylaluminoxane having less than 50 mole percent and 11 mole percent or more of AlR A1 R B1 R C1 based on the total moles of aluminum in the hydrocarbyl-modified methylaluminoxane, wherein R A1 、R B1 and R C1 are independently linear C 1 -C 40 alkyl, branched C 1 -C 40 alkyl, or C 6 -C 40 aryl, and One or more metal-ligand complexes according to formula (I): Wherein: m is titanium, zirconium or hafnium; n is 1, 2 or 3; Each X is independently selected from C 1 −C 20 hydrocarbyl, phenyl, benzyl, and halogen; The metal-ligand complex as a whole is electrically neutral; R 1 and R 16 are independently selected from the group consisting of radicals having formula (II), radicals having formula (III) and radicals having formula (IV): Wherein each of R 31-35 、R 41-48 and R 51-59 is independently selected from-H, C 1 −C 20 hydrocarbyl, -Si [ C 1 −C 20 hydrocarbyl ] 3 、−Si(R C ) 3 、−OR C 、−SR C 、−CN、−CF 3 or halogen; R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 And R 15 is independently selected from-H, C 1 −C 40 hydrocarbyl, C 1 −C 40 heterohydrocarbyl, -Si (R C ) 3 、−OR C 、−SR C 、−CN、−CF 3 and halogen; Y is CH 2 、CHR 21 、CR 21 R 22 、SiR 21 R 22 or GeR 21 R 22 , wherein R 21 and R 22 are C 1 -C 20 alkyl; The preconditions are that: (1) Y is CH 2 , at least one of R 8 and R 9 is not-H; R C is independently C 1 −C 30 hydrocarbyl, C 1 −C 30 heterohydrocarbyl or-H, and Wherein the catalyst system is free of borate activators.
  2. 2. The polymerization process of claim 1, wherein the hydrocarbyl-modified methylaluminoxane contains less than 25 mole percent AlR A1 R B1 R C1 based on the total moles of aluminum in the hydrocarbyl-modified methylaluminoxane.
  3. 3. The polymerization process of claim 1, wherein the hydrocarbyl-modified methylaluminoxane is a modified methylaluminoxane.
  4. 4. The polymerization process of claim 1, wherein at least one of R 8 and R 9 is a C 1 −C 40 hydrocarbyl, C 1 −C 40 heterohydrocarbyl, or halogen atom.
  5. 5. The polymerization process of claim 1, wherein at least one of R 8 and R 9 is C 1 −C 5 alkyl.
  6. 6. The polymerization process of claim 1, wherein at least one of R 1 and R 16 is a radical having formula (III).
  7. 7. The polymerization process of claim 6, wherein R 42 and R 47 are C 1 −C 20 hydrocarbyl or-Si [ C 1 −C 20 hydrocarbyl ] 3 , or R 43 and R 46 are C 1 −C 20 hydrocarbyl or-Si [ C 1 −C 20 hydrocarbyl ] 3 .
  8. 8. The polymerization process of claim 1, wherein at least one of R 1 and R 16 is a radical having formula (II).
  9. 9. The polymerization process of claim 8, wherein R 32 and R 34 are C 1 −C 12 hydrocarbyl or-Si [ C 1 −C 20 hydrocarbyl ] 3 .
  10. 10. The polymerization process of claim 1, wherein at least one of R 1 and R 16 is a radical having formula (IV).
  11. 11. The polymerization process of claim 10, wherein at least two of R 52 、R 53 、R 55 、R 57 and R 58 are C 1 −C 20 hydrocarbyl or-Si [ C 1 −C 20 hydrocarbyl ] 3 .
  12. 12. The polymerization process of claim 1, wherein R 3 and R 14 are C 1 −C 20 alkyl.
  13. 13. The polymerization process of claim 1, wherein R 6 and R 11 are t-butyl.
  14. 14. The polymerization process of claim 1, wherein R 3 and R 14 are t-octyl or n-octyl.
  15. 15. The polymerization process of claim 1, wherein the olefin monomer is a C 3 −C 20 a-olefin.
  16. 16. The polymerization process of claim 1, wherein the olefin monomer is a cyclic olefin.
  17. 17. The polymerization process of claim 1, wherein the polymerization process is a solution polymerization reaction.

Description

Hydrocarbon-modified methylaluminoxane cocatalyst of diphenyl phenoxy metal-ligand complex Cross Reference to Related Applications The present application claims priority from U.S. provisional patent application No. 63/053,354, filed 7/17/2020, the entire disclosure of which is hereby incorporated by reference. Technical Field Embodiments of the present disclosure generally relate to modified hydrocarbyl methylaluminoxane activators for catalyst systems comprising a diphenylphenoxy metal-ligand complex having a three atom ether linker. Background Since the discovery of heterophasic olefin polymerization by Ziegler and nati, global polyolefin production reaches about 1.5 hundred million tons per year in 2015 and rises due to the increasing market demand. This success is based in part on a series of important breakthroughs in the promoter technology. Promoters found include aluminoxanes, boranes and borates with triphenylcarbonium or ammonium cations. These cocatalysts activate homogeneous single-site olefin polymerization catalysts and have been used industrially to produce polyolefins. The activator may have characteristics that facilitate the production of the-olefin polymer and the final polymer composition comprising the a-olefin polymer as part of the catalyst composition in the polymerization of the a-olefin. Activator characteristics that increase the yield of alpha-olefin polymer include, but are not limited to, rapid procatalyst activation, high catalyst efficiency, gao Chengwen capacity, consistent polymer composition, and selective deactivation. Borate-based cocatalysts are particularly useful for a fundamental understanding of the mechanism of olefin polymerization and enhance the ability to precisely control polyolefin microstructure by purposeful adjustments of catalyst structure and process. This has led to an interest in the excitation of mechanism studies and to the development of novel homogeneous olefin polymerization catalyst systems with precise control over polyolefin microstructure and properties. However, once the cations of the activator or cocatalyst activate the procatalyst, the ions of the activator may remain in the polymer composition. As a result, borate anions may affect polymer composition. In particular, the size of the borate anion, the charge of the borate anion, the interaction of the borate anion with the surrounding medium, and the dissociation energy of the borate anion from the available counter-ions will affect the ability of the ions to diffuse through the surrounding medium (e.g., solvent, gel, or polymeric material). Modified Methylaluminoxane (MMAO) can be described as a mixture of aluminoxane structures and trihydrocarbylaluminum species. Trihydrocarbylaluminum materials such as trimethylaluminum are used as scavengers to remove impurities that may cause deactivation of the olefin polymerization catalyst during polymerization. However, it is believed that the tri-hydrocarbyl aluminum species may be active in some polymerization systems. Catalyst inhibition was noted when trimethylaluminum was present in the propylene homopolymerization at 60 ℃ with hafnocene catalyst (Busico, v. Et al macromolecules 2009,42,1789-1791). However, these observations suggest a difference between MAO activation and borate activation, and even in direct comparison only some of the differences between trimethylaluminum and no trimethylaluminum might be captured. In addition, it is not clear whether these observations extend to other catalyst systems, ethylene polymerizations or polymerizations conducted at higher temperatures. Regardless, the preference for soluble MAO requires the use of MMAO and thus the presence of a tri-hydrocarbyl aluminum species. Modified Methylaluminoxane (MMAO) is used as an activator in some PE processes instead of borate based activators. However, MMAO has been found to have a negative impact on the performance of some catalysts (e.g., bis-biphenylphenoxy metal-ligand complexes) and negatively impact the production of polyethylene resins, including reducing catalyst activity, widening the resulting polymer composition distribution, and negatively impacting pellet handling. Disclosure of Invention There is a continuing need to produce a catalyst system while maintaining catalyst efficiency, reactivity, and the ability to produce polymers with good physical properties. There is also a need to produce a uniform polymer composition. Embodiments of the present disclosure include a method of polymerizing an olefin monomer. In one or more embodiments, the process comprises reacting ethylene and optionally one or more olefin monomers in the presence of a catalyst system. The catalyst system comprises a modified alkyl methyl aluminoxane and a main catalyst. A modified hydrocarbylmethylaluminoxane having less than 50 moles of AlR ARBRC, based on total moles of aluminum, wherein R A、RB and R C are independently linear (C 1-C40) alkyl, branched (C 1-C40) alkyl, or (C 6-