|371. Millard, P.-E.; Barner, L.; Reinhardt, J.; Buchmeiser, M.R.; Barner-Kowollik, C.; Müller, A.H.E.: Synthesis of water-soluble homo- and block-copolymers by RAFT polymerization under γ-irradiation in aqueous media, Polymer 51(19), 4319 (2010) -- DOI: 10.1016/j.polymer.2010.07.017|
|Key words: Reversible addition fragmentation chain transfer (RAFT), Water-soluble polymers, Stimuli-responsive polymers|
The ambient temperature (20 °C) reversible addition-fragmentation chain transfer (RAFT) polymerization of several water-soluble monomers conducted directly in aqueous media under γ-initiation (at dose rates of 30 Gy h-1) proceeds in a controlled fashion. Using functional trithiocarbonates, i.e., S,S-bis(α,α'-dimethyl-α"-acetic acid)trithiocarbonate (TRITT), 3-benzylsulfanyl thiocarbonylsulfanyl propionic acid (BPATT), and dithioester, i.e., 4-cyanopentanoic acid dithiobenzoate (CPADB), as chain transfer agents, fully water-soluble polymers of monomers such as N,N-dimethylacrylamide, 2-hydroxyethyl acrylate, acrylamide or oligo(ethylene glycol) methacrylate and stimuli-responsive polymers of monomers such as acrylic acid, N-isopropylacrylamide, 2-(dimethylamino)ethyl methacrylate or 2-acrylamido-2-methylpropane sulfonic acid can be obtained over a wide range of degrees of polymerization up to 10,000 with low polydispersity (typically < 1.2) to near quantitative conversions. Well-defined block copolymers between these monomers, based on several asymmetric macro-RAFT agents, can be obtained, suggesting that the RAFT agents are stable throughout the polymerization process so that complex and well-defined architectures can be obtained.
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