Combining catalytic chain transfer polymerisation and post-polymerisation functionalisation for the preparation of functional materials

The initial objective of this thesis was to synthesis amphiphilic polymethacrylates under the umbrellas of catalytic chain transfer polymerisation and click-chemistry that could then be used as dispersing agents in carbon black waterborne suspensions. Three generations of dispersants were iteratively synthesised and tested. MKI and MKII (chapter 1) dispersants were prepared through the polymerisation of glycidyl methacrylate and glycerol monomethacrylate respectively. In the former, amphiphilic polymers were prepared using an optimised one-pot dual post-polymerisation consisting of Michael-thiol addition of commercially available hydrophobic mercaptans, followed by microwave-assisted epoxide ring-opening. It was found that most polymers were fully functionalised within a 3-hour window, with minimal side-reactions. For MKII dispersants, the epoxide ring-opening step was bypassed, with Michael-thiol additions reaching full conversion within 5 minutes The third generation, MKIII (chapter 2), allowed us to consider various aspects of our protocol and how to improve its environmental friendliness. Glycerol monomethacrylate synthesis was carried out in green solvents such as IPA. Functionalisation of the macromonomers was subsequently investigated with amines, through aza-Michael addition, under three synthetic pathways: catalysed, catalyst-free, and catalyst-free microwave-assisted (MAOS). This allowed the investigation of various reaction conditions and, two final dispersant candidates with nonyl- and dodecylamine anchors were prepared through catalyst-free MAOS. The various amphiphilic polymethacrylates’ (MKI: 12 candidates, MKII: 8 candidates and MKIII: 2 candidates) performance as stabilising agent in carbon black waterborne pigment suspensions were tested in chapter 4. In our investigations, stabilising segment with a molecular weight of 1-2.5 kDa were determined to provide better stabilisation. Furthermore, it was not only found that linear aliphatic anchors would adsorb better onto the surface of other pigment than any other type of anchor, but also that these dispersants would outperform commercially available products. We also wished to investigate new applications of CCTP (chapter 5). To this end, EGDMA-based branched CCT-macromonomers were integrated as crosslinkers into polyHIPE formulations. The use of various acrylate propagation promoters such as 2-ethylhexyl acrylate (EHA), isobornyl acrylate (IBOA) and 2-methoxyethyl acrylate (MEA) was shown to both facilitate the photochemical curing of the HIPEs and to impart material properties to the products. Scanning electron microscopy (SEM) was used to explore the morphology of the materials. Surface wettability experiments were conducted to evaluate the hydrophilicity of the polyHIPEs’ surface and, compression tests were used to investigate the influence of the branching density of the CCTP macromonomers, as well as the nature of promoters on the mechanical properties of the prepared polyHIPEs