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Title:Engineering approaches to control polymer architecture
Author(s):Walsh, Dylan
Director of Research:Guironnet, Damien
Doctoral Committee Chair(s):Guironnet, Damien
Doctoral Committee Member(s):Moore, Jeffrey S.; Kenis, Paul J. A.; Sing, Charles E.
Department / Program:Chemical & Biomolecular Engr
Discipline:Chemical Engineering
Degree Granting Institution:University of Illinois at Urbana-Champaign
Degree:Ph.D.
Genre:Dissertation
Subject(s):Polymers
Flow Chemistry
Bottlebrush Polymers
Molecular Weight
Size Exclusion Chromatography
Ring Opening Metathesis Polymerization
ROMP
Abstract:The synthesis of well-defined polymers offers great potential for improving society as there is nearly an infinite spectrum of tailored materials that can be made. Traditionally, the polymer community has mainly focused on purely chemistry driven methods for controlling polymer molecular weight, composition, topology, tacticity, and temporal and spatial patterning. However, my work has sought to approach polymer synthesis with hybrid solutions of the latest research in chemistry with the fundamentals of engineering like automation, fluid mechanics, and reactor design. This approach to polymer synthesis provides simple, efficient, and precise methodologies to access a wide array of well-defined materials. Chapter 1 will review the recent trends in controlled polymer synthesis. This chapter provides an overview on molecular weight, composition, topology, tacticity, and temporal and spatial control. Chapter 2 will cover the development of a methodology to incorporate polyolefins into functionalized (polar and non-polar) block copolymers. This general methodology is based on a catalytic post-polymerization functionalization method that is shown to be compatible with any polyolefin. Chapter 3 will cover the kinetic and mechanistic studies of ring opening metathesis polymerization with third generation Grubbs catalyst. This chapter provides the mechanistic origins of the unique zero order kinetics of the third generation Grubbs catalyst, and details the implementation of this for polymer synthesis. Chapter 4 will cover the design of polymer molecular weight distributions through flow chemistry. This chapter describes the first methodology that enables the direct ‘design to synthesis’ of polymer molecular weight distributions, which was enabled by fundamental researching into reactor design for polymerization flow reactors. Chapter 5 will cover the engineering of molecular geometry in bottlebrush polymers. This chapter describes the development of two reactor based approaches for the synthesis of non-cylindrical bottlebrushes; the first approach is a semi-batch reactor, while the second approach implements a flow-reactor. Chapter 6 will cover the challenges of size exclusion chromatography for the analysis of bottlebrush polymers. This chapter is a culmination of critical data analysis and practical information to help improve the rigor of polymer characterization by size exclusion chromatography to support the development of structure function relationships.
Issue Date:2020-04-22
Type:Thesis
URI:http://hdl.handle.net/2142/108262
Rights Information:Copyright 2020 Dylan J. Walsh
Date Available in IDEALS:2020-08-27
Date Deposited:2020-05


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