Nanoporous and Functionalized Polymer Thermosets by Polymerization-Induced Microphase Separation in Bulk, Dilution, and Suspension

Abstract

The microphase separation of diblock polymers allows for excellent control over the nanostructuring of polymer-based materials. Polymers are also readily functionalized and chemically manipulated to alter their chemical properties. Therefore, block polymers represent an important tool in the preparation of precision nanostructured functional materials. Polymerization-induced microphase separation (PIMS) is a convenient and powerful strategy towards the development of such materials. In PIMS, the diblock polymer is simultaneously grown while one block is crosslinked. This captures a non-equilibrium percolating morphology. In this thesis, the morphology is used as a host for photochromic dyes, diluted with solvent to increase the possible porosity, and prepared in suspension to give uniform mesoporous beads.Chapter 1 is a brief overview of key topics relevant to the entire thesis. Chapter 2 describes the incorporation of photochromic dye molecules into a variety of materials from liquid solvent to rigid polymer. PIMS thermosets were created using a liquid-like polycaprolactone derivative and crosslinked polymethylmethacrylate. The liquid-like domains provide an environment for the dye where fast structural relaxation allows for fast dye decoloration while being encased in a rigid matrix. Chapter 3 shifts focus to porous PIMS derivatives. In particular, the effect on the pore size distribution of diluting the monomer solution with solvent to create an organogel is explored. Chapter 4 presents a new synthetic method to prepare beads from PIMS thermosets by performing the chain-growth and cross-linking steps in aqueous suspension. The size of the particles is tuned independently from the size of the pores. Also, functionality is incorporated into the pore walls using a diblock precursor. Chapter 5 provides general conclusions and possible future directions for research relating to disordered diblock thermoset materials.