3 years ago

Fusing Light-Induced Step-Growth Processes with RAFT Chemistry for Segmented Copolymer Synthesis: A Synergetic Experimental and Kinetic Modeling Study

Fusing Light-Induced Step-Growth Processes with RAFT Chemistry for Segmented Copolymer Synthesis: A Synergetic Experimental and Kinetic Modeling Study
Anja S. Goldmann, Christopher Barner-Kowollik, Dagmar R. D’hooge, Paul H. M. Van Steenberge, Jan O. Mueller, Lies De Keer, Jan P. Menzel, Thomas Gegenhuber, Marie-Françoise Reyniers
We pioneer the synthesis of well-defined high molar mass segmented copolymers, employing a unique combination of step-growth and reversible addition–fragmentation chain transfer (RAFT) polymerization. The step-growth precursor polymer is obtained via the ambient temperature UV-light-induced Diels–Alder reaction of 6′-(propane-1,3-diylbis(oxy))bis(2-methylbenzaldehyde) (AA monomer) and di(isopropionic ethyl ester fumarate) trithiocarbonate (BB monomer). Unconventional off-stoichiometric conditions (r = [AA]0:[BB]0 = 1.5–1.75) are employed to ensure a sufficiently high incorporation of BB in the step-growth product (1200 ≤ Mn/g mol–1 ≤ 3950). The optimum r value is based on a detailed product distribution analysis, comparing experimental and bivariate kinetic Monte Carlo generated data, using a scheme of over 200 reactions. The analysis highlights the unexpected occurrence of AA homopolymerization and the ligation of the resulting AA segments at higher reaction times. The precursor step-growth polymer is successfully transformed into a segmented copolymer via insertion of styrene by RAFT polymerization at 60 °C (11 200 ≤ Mn/g mol–1 ≤ 53 400), as confirmed both experimentally and through simulations.

Publisher URL: http://dx.doi.org/10.1021/acs.macromol.7b01394

DOI: 10.1021/acs.macromol.7b01394

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