Identification and quantification of structural defects in 13C- and 2H-labeled Gilch and sulphinyl MDMO-PPV - A correlation between chemical structure and molecular dynamics and ordering by modern NMR spectroscopy

Abstract

A thorough knowledge of the chemical structure – physical properties relationship is the main objective of this research project. Understanding the factors influencing the opto-electronic properties especially the synthetic procedures used, may provide the means to enhance the efficiency of the opto-electronic devices. In chapter two, the basic principles of nuclear magnetic resonance spectroscopy (NMR) are described. Throughout this work, NMR spectroscopy has proven to be a powerful and indispensable tool, not only to elucidate the polymer structure, but also to provide insight into the molecular ordering and dynamics of polymer chains. The type and amount of structural defects present in the 13C-labeled MDMO-PPV synthesized according to the sulphinyl and Gilch precursor route are discussed in chapter three. In chapter four, the various solid state NMR techniques used to study the molecular chain mobility and ordering of the sulphinyl and Gilch MDMO-PPV polymers are explained. The chain dynamics of MDMO-PPV during the elimination reaction is examined by means of 1H wideline NMR spectroscopy in chapter 5. The molecular ordering and dynamics of the Gilch and sulphinyl synthesized MDMO-PPVs are examined in chapter 6 by means of 2H wideline, 13C wideline, 1H wideline and high-resolution 13C CP/MAS with high power proton dipolar decoupling NMR spectroscopy. Furthermore, the morphology was studied by applying some WAXS, DSC and rheology measurements. The synthesis of the 13C- and 2H-labeled polymers, as well as the experimental conditions of the analytical techniques are mentioned in chapter seven. Finally, a short summary, general conclusions and perspectives are given in English (chapter eight) and Dutch(chapter nine),respectively. In chapter 10, a list of abbreviations is mentioned.