Atom Transfer Radical Polymerization with Low Catalyst Concentration in Continuous Processes

Abstract

Atom transfer radical polymerization (ATRP) is a dynamic technique that possesses tremendous potential for the synthesis of novel polymeric materials not possible through conventional free radical polymerization. However, its use on an industrial scale has been limited by the high level of transition metal complex required. Significant advances have been made in the last 5 years towards lowering the level of copper complexes used in ATRP, resulting in novel variants called “activator regenerated by electron transfer” (ARGET) and “single electron transfer-living radical polymerization” (SET-LRP). To fully realize the potential of ATRP, its use in industrially relevant processes must be studied. Continuous processes such as tubular flow reactors and stirred tank reactors (CSTR) can reduce waste, improve productivity and facilitate process scale-up when compared to common batch reactors. The combination of low copper concentration ATRP techniques and continuous processes are especially attractive towards the design of a commercially viable process. This thesis presents a study into ARGET ATRP and SET-LRP as applied to continuous tubular and stirred tank reactors for the production of acrylic and methacrylic polymers. The equilibrium which governs polymerization rate and control over molecular architecture is studied through batch ARGET ATRP experiments. The improved understanding of ARGET ATRP enabled the reduction of ligand from a 3 to 10 fold excess used previously down to a stoichiometric ratio to copper salts. ARGET ATRP was then adapted to a continuous tubular reactor, as well as to a semi-automated CSTR. The design of the reactors and the effect of reaction conditions such as reducing agent concentration and residence time are discussed. The use of common elemental copper(0) such as copper wire and copper tubing is also investigated with SET-LRP for room temperature polymerization of methyl acrylate. SET-LRP is adapted to a CSTR to observe the effects of residence time on reaction rate, molecular weight control as well as copper consumption rate. The use of copper tubing as a catalyst source for SET-LRP is demonstrated and the design of a continuous tubular reactor using a combination of copper and stainless steel tubing is discussed.