Photo-induced copper-mediated radical polymerization of methyl acrylate (MA) is carried out in DMSO at 15 C in a tubular photo-flow reactor as well as in a glass-chip based microreactor. Polymerization reactions proceed rapidly to approximately 90% monomer conversion within 20 minutes of reactor residence time.Control of reactions is high as evidenced by ideal polymerization kinetics, low dispersities of the obtained polymers (in the range of 1.1) and linear evolution of number average molecular weights during polymerization reactions. Poly(MA) with average molecular weights between a few hundred and $5000 g mol À1 was obtained under retention of pristine end group fidelity. Besides homopolymers, block copolymers can also be successfully synthesized and poly(methyl acrylate)-b-poly(butyl acrylate) block copolymers with a similar low dispersity are obtained. Reactions proceed under homogeneous reaction conditions. This feature allows the reaction to be carried out in milli-and also in microflow devices. In both cases, equally good control is achieved with only minimal adaptation of the reaction protocol, underpinning the simplicity and fast adaptability of the protocol to different flow reactors.

Precision polymer design in continuous photoflow reactors is a young, yet rapidly growing research field. The potential of photopolymerization is demonstrated and future potential is discussed.

The Arrhenius parameters of the propagation rate coefficient, kp , are determined employing high-frequency pulsed laser polymerization-size exclusion chromatography (PLP-SEC) for the homologous series of five linear alkyl acrylates (i.e., methyl acrylate (MA), butyl acrylate (BA), dodecyl acrylate (DA), stearyl acrylate (SA), and behenyl acrylate (BeA)) in 1 m solution in butyl acetate (BuAc) as well as in toluene. The comparison of the obtained kp values with the literature known values for bulk demonstrates that no significant solvent influence neither in BuAc nor in toluene on the propagation reaction compared to bulk is detectable. Concomitantly, the kp values in toluene and in BuAc solution display a similar increase with increasing number of C-atoms in the ester side chain as was previously reported for the bulk systems. These findings are in clear contrast to earlier studies, which report a decrease of kp with increasing ester side chain length in toluene. The additional investigation of the longest and shortest ester side chain acrylate (i.e., BeA and MA) over the entire experimentally available concentration range at one temperature (i.e., 50 °C) does not reveal any general concentration dependence and all observed differences in the kp are within the experimental error.

Photo-induced copper-mediated polymerization (photoCMP) is employed for the synthesis of multiarm-multiblock star copolymers. Based on a core-first approach, star polymers with four, six and twenty-one arms have been synthesized.