Reversible addition fragmentation chain transfer (RAFT) of a new class of pH-sensitive monomers and polymerization induced self-assembly (PISA) in supercritical carbon dioxide
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Chapter 1 The traditional thermal Mannich reaction is unsuitable for preparing polymerizable N-methylene amino substituted acrylamides and methacrylamides. Herein we provide a facile multi-gram high yield synthesis of these monomeric precursors to stimuli-responsive polymers by addition of acrylamide and methacrylamide onto in situ generated or freshly isolated methylene Schiff base (iminium) salts. The synthetic methodology developed in synthesizing building blocks for smart polymers is described in context with the chemical literature. An Experimental section describes gram-scale syntheses of monomers. Parts of this chapter were published in Organic & Biomolecular Chemistry, 2018, 16, 4108–4116. Chapter 2 Begins with an introduction to Reversible Addition Fragmentation Chain Transfer (RAFT). The previously elusive N-[cycloamino)methyl]acrylamides monomer class prepared in Chapter 1 is subjected to the first controlled/living polymerizations, which gave water-soluble well-defined polyacrylamide triblock copolymers. . An Experimental section describes the RAFT procedures in detail from poly(N,N-dimethylacrylamide) macro-RAFT. Parts of this chapter were published were published in J. Polym. Sci., Part A: Polym Chem. 2017, 55, 2123–2128. Chapter 3 Begins with an introduction to Atom Transfer Radical Polymerization (ATRP) and an overview of the literature on Polymerization Induced Self-Assembly (PISA), and controlled/living dispersion polymerizations in the benign polymerization medium, supercritical carbon dioxide (scCO2). The results and discussion presented are yet to be published; describing the first PISA in scCO2 to give higher order non-spherical objects, namely rods and vesicles. PISA in scCO2 was implemented using ATRP of benzyl methacrylate (BzMA) using a dispersion polymerization from poly(dimethylsiloxane, DMS) bromide macroinitiator. Giant rods and vesicles up to 30 µm in length were produced at the highest degrees of polymerization and the highest solids content.