Title

Synthesis and characterization of polymeric materials derived from multifunctional alkyl alpha-hydroxymethlacrylates

Date of Award

2008

Degree Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Polymers and High Performance Materials

First Advisor

Lon Mathias

Advisor Department

Polymers and High Performance Materials

Abstract

The research presented in this dissertation covers the investigation of new materials derived from alkyl α-hydroxymethylacrylates (RHMA). The first project exposed in Chapter II involves the synthesis, characterization of RHMA-based reactive surfactants and their successful incorporation in acrylic latexes. The amphiphilic monomers testify of a good copolymerization behavior with other acrylic monomers such as methyl methacrylate and butyl acrylate although their extensive bulkiness. They led to the formation of well-defined polymeric particles via a seeded emulsion polymerization process and permitted decreasing significantly the water sensitivity of the resulting films as compared to film incorporating conventional emulsifier such as sodium dodecyl sulfate. The research presented in Chapter III focuses of the use of such reactive surfactant as compatibilizer in polymer/TiO2 nanocomposites. Their incorporation led to an increase in the overall UV-absorption properties of the resulting polymeric materials correlated by an enhancement of filler dispersion within the matrix. The synthesis, characterization of RHMA-based cationic surfmers is discussed in Chapter IV. Their incorporation in poly(methyl methacrylate)/clay nanocomposites as compatibilizers is studied and the impact of the polymerization technique and of the film formation method used on the composite's properties investigated. Emulsion polymerization led to enhanced filler dispersion when a solvent-casting method was used to form the corresponding film. Chapter V describes the synthesis and polymerization of alkyl 2-carboethoxyhydroxymethylacrylates. Such alkenes display interesting reactivity in radical polymerization compared to other hindered RHMA analogs however, the resulting homo- and copolymers still testify of low yields and molecular weights. This behavior is attributed to some degree of chain transfer to monomer that may involve the allylic proton. Chapter VI presents the synthesis of polyfunctional 2-pyrrolidinone derivatives from a variety of new alkyl 2-carboethoxyhydroxymethylacrylates via a very efficient Michael addition/cyclization reaction sequence. Fast, clean, quantitative, and leading to compounds with no need for subsequent purification, this "click" reaction opens up a brand new synthetic window to the preparation of new optically active derivatives. The preparation of new 2-pyrrolidinone acid derivatives is described in Chapter VII. The separation of the cis and trans isomers composing the resulting product were successfully separated by simple recrystallization technique. The study of hydrogen bonding interactions intrinsic of such heterocycle allowed confirming the respective isomer structures. The synthesis and photopolymerization kinetics of new pyrrolidinone methacrylate monomers are described in Chapter VIII as well as the characterization of the corresponding homopolymers. The importance of hydrogen-bonding interactions in the polymerization kinetics as well as on the final polymer properties are discussed. Responsible for enhancing the polymerization rate of the pyrrolidinone-containing monomers prepared, hydrogen-bonding interactions led to the apparition of a pseudo beta transition for the resulting homopolymers. Chapter IX involves the synthesis of bis-pyrrolidinone acid derivatives. It was found that such derivatives display Tg s during thermal analysis. This polymer-like behavior is attributed to non-covalent supramolecular associations. The final part of this dissertation involves the kinetics study of the Michael addition/cyclization reaction sequence and polymerization involving alkyl 2-carboethoxyhydroxymethylacrylates and primary amines. This new polymerization route led to the formation of a new class of poly(ester amide)s with potential applications as biodegradable coatings.