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Title:Development of synthetic methodologies for polyolefin containing block copolymers
Author(s):Yan, Tianwei
Director of Research:Guironnet, Damien S.
Doctoral Committee Chair(s):Guironnet, Damien S.
Doctoral Committee Member(s):Kenis, Paul J.A.; Sing, Charles E.; Fout, Alison R.
Department / Program:Chemical & Biomolecular Engr
Discipline:Chemical Engineering
Degree Granting Institution:University of Illinois at Urbana-Champaign
Degree:Ph.D.
Genre:Dissertation
Subject(s):polyolefin
post-polymerization modification
block copolymer
selective copolymerization
Abstract:Polyolefins and block copolymers are two important groups of polymeric materials. On one end, polyolefins are the most commonly produced polymers, as a representative of polymers that have transformed our everyday life. On the other end, block copolymers are specialty materials that are produced at much smaller scales. With unique and well-defined chemical structures, block copolymers result in unmatched properties. However, the synthetic challenge hinders the combination of the two fields. Here my work has proposed a complete set of approaches to end-functionalize polyolefins with post-polymerization modification and selective copolymerization strategies. The strategies enable simple, selective and productive approaches to access well-defined amphiphilic diblock and triblock copolymers containing both polyolefin blocks and polar blocks. Chapter 1 will state the problem and review the previous literature about the synthesis of telechelic polyolefins. This chapter provides an overview of the state-of-the-art strategies in order to obtain telechelic polyolefin, as the key precursor to access polyolefin-containing multiblock copolymers. Chapter 2 will cover the development of a one-pot methodology to access polyolefin-containing diblock copolymers. This general methodology is based on a catalytic tandem hydroformylation/hydrogenation reaction applicable to any polyolefin. Chapter 3 will cover the synthesis of polyethylene-containing triblock copolymers. As an extension of the end-functionalization methodology from chapter 2, the proposed post-polymerization functionalization succeeded in introducing one functionality both randomly in the middle of the polymer backbone and at one chain end, eventually leading to the branched polyethylene-containing triblock copolymer, or 3-miktoarm star. Chapter 4 will cover the design of isotactic polypropylene-containing triblock copolymers. Selective copolymerization strategy was adopted during the synthesis of telechelic polypropylene as the precursor, in order to maintain the stereoregularity of the backbone while also get precise control of the chain-end structure. The desired polypropylene-containing triblock copolymers were then accessed by post-polymerization modification.
Issue Date:2021-04-07
Type:Thesis
URI:http://hdl.handle.net/2142/110790
Rights Information:Copyright 2021 Tianwei Yan
Date Available in IDEALS:2021-09-17
Date Deposited:2021-05


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