Improved Mechanistic Insights into Radical Sulfinyl Precursor MDMO-PPV Synthesis by Combining Microflow Technology and Computer Simulations

Abstract

A kinetic model using Predici is developed and applied to obtain an improved mechanistic understanding of the radical sulfinyl precursor polymerization route for poly(2-methoxy-5-(3′-7′-dimethyloctyloxy-4-((octylsulfinyl)methyl))-1,4-phenylenevinylene) (MDMO-PPV) synthesis. In this route, the premonomer—1-(chloromethyl)-5-((3,7-dimethyloctyl)oxy)-2-methoxy-4-((octylsulfinyl)methyl) benzene (MDMO)—is subjected to a base-induced elimination reaction using NatBuO as base and s-BuOH as solvent. Microreactors are used to ensure rapid mixing of reaction components and sharp quenching at precisely determined time points. Systematic kinetic data that follows the very fast precursor polymerizations with reaction time have in this way become available for the first time. Via the applied kinetic model, the presence of a chain transfer reaction is unambiguously confirmed and kinetic rate coefficients have been deduced, which fall within the typical expectations of radical chain reactions. Two models were further comp...