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Insertion of Olefins into Nickel Alkyl Complexes: Mechanistic Studies and Polymerization Catalysis


Xiong, Shuoyan (2023) Insertion of Olefins into Nickel Alkyl Complexes: Mechanistic Studies and Polymerization Catalysis. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/n59w-qg36.


Polyolefins account for over half of global plastic production. The incorporation of polar functionalities can provide value-added polyolefins with desirable material properties and potential degradability. To achieve this, coordination copolymerization of ethylene and fundamental polar comonomers by transition-metal catalysts is the most direct, economical, and environmentally friendly method. Though it has been pursued for decades, the catalyst performance (e.g. activity, thermal stability) is still far below practical thresholds. The major issue is the "polar monomer problem": coordination of the polar group in the comonomer to the metal center competes with vinyl coordination, a prerequisite for the monomer enchainment (chain propagation).

This thesis describes mechanism-driven developments of industrially applicable molecular catalysts toward addressing the "polar monomer problem", with a focus on nickel catalysts for ethylene/acrylate copolymerization.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Catalysis, organometallic synthesis, nickel, functional polyolefins, mechanistic interrogation, olefin polymerization, acrylates, ethylene, coordination polymerization, reactivity studies, spectroscopy, multimetallic catalysts, base metal catalysis
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Agapie, Theodor
Thesis Committee:
  • Gray, Harry B. (chair)
  • Peters, Jonas C.
  • Robb, Maxwell J.
  • Agapie, Theodor
Defense Date:10 January 2023
Funding AgencyGrant Number
Dow Chemical CompanyUNSPECIFIED
Record Number:CaltechTHESIS:03282023-190134907
Persistent URL:
Related URLs:
URLURL TypeDescription adapted for ch. 2 adapted for ch. 3 adapted for ch. 4 adapted for ch. 5
Xiong, Shuoyan0000-0002-2579-4260
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:15125
Deposited By: Shuoyan Xiong
Deposited On:26 May 2023 22:19
Last Modified:08 May 2024 16:33

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