Facile Synthesis of Well-Defined MDMO-PPV Containing (Tri)Block-Copolymers via Controlled Radical Polymerization and CuAAC Conjugation

A systematic investigation into the chain transfer polymerization of the so-called radical precursor polymerization of poly(p-phenylene vinylene) (PPV) materials is presented. Polymerizations are characterized by systematic variation of chain transfer agent (CTA) concentration and reaction temperature. For the chain transfer constant, a negative activation energy of -12.8 kJ center dot mol(-1) was deduced. Good control over molecular weight is achieved for both the sulfinyl and the dithiocarbamate route (DTC). PPVs with molecular weights ranging from thousands to ten thousands g center dot mol(-1) were obtained. To allow for a meaningful analysis of the CTA influence, Mark-Houwink-Kuhn-Sakurada (MHKS) parameters were determined for conjugated MDMO-PPV ([2-methoxy-5-(3',7'-dimethyloctyloxy)]-1,4-phenylenevinylene) to alpha = 0.809 and k = 0.00002 mL center dot g(-1). Further, high-endgroup fidelity of the CBr4-derived PPVs was proven via chain extension experiments. MDMO-PPV-Br was successfully used as macroinitiator in atom transfer radical polymerization (ATRP) with acrylates and styrene. A more polar PPV counterpart was chain extended by an acrylate in single-electron transfer living radical polymerization (SET-LRP). In a last step, copper-catalyzed azide alkyne cycloaddition (CuAAC) was used to synthesize block copolymer structures. Direct azidation followed by macromolecular conjugation showed only partial success, while the successive chain extension via ATRP followed by CuAAC afforded triblock copolymers of the poly(p-phenylene vinylene)-block-poly(tert-butyl acrylate)-block-poly(ethylene glycol) (PPV-b-PtBuA-b-PEG).