Molecular brushes based on copolymers of alkoxy oligo(ethylene glycol) methacrylates and dodecyl(meth)acrylate: features
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Molecular brushes based on copolymers of alkoxy oligo(ethylene glycol) methacrylates and dodecyl(meth) acrylate: features of synthesis by conventional free radical polymerization Dmitry V. Orekhov1 · Denis M. Kamorin1,2 · Alexander S. Simagin1 · Ildar R. Arifullin1 · Oleg A. Kazantsev1 · Alexey P. Sivokhin1 · Maria V. Savinova1 Received: 1 June 2020 / Revised: 22 August 2020 / Accepted: 24 September 2020 © Springer-Verlag GmbH Germany, part of Springer Nature 2020
Abstract Amphiphilic copolymer molecular brushes of three different types with side chains consisting of alkyl and oligo(ethylene glycol) blocks based on higher alkoxy oligo(ethylene glycol) methacrylates (HAOEGM), methoxy oligo(ethylene glycol) methacrylates (MOEGM) and dodecyl(meth)acrylate have been successfully synthesized via conventional radical polymerization in toluene. In case of the copolymerization of HAOEGM with MOEGM, the monomer reactivity ratios were independent of the structure of higher alkyl groups (C12–C18) and the degree of ethoxylation (n = 6–11) and were equal to 0.76–0.81 and 1.19–1.27, respectively. In case of the copolymerization of HAOEGM or MOEGM with dodecyl methacrylate, the reactivity ratios were even closer to each other (1.00–1.17). Applicability of the reactivity ratios calculated at low conversions for estimating copolymer compositions at high conversions was shown. In all systems, compositionally homogeneous copolymers with a narrow molecular weight distribution were formed. For the HAOEGM (C12, n = 9)—dodecyl acrylate monomer system, the reactivity ratios were 0.88 and 0.25 and the resulting copolymers had high compositional heterogeneity. Keywords Alkoxy oligo (ethylene glycol) methacrylates · Methoxy oligo (ethylene glycol) methacrylates · Amphiphilic polymers · Molecular brushes · Radical copolymerization · Monomer reactivity ratios · Copolymer composition heterogeneity
* Dmitry V. Orekhov [email protected] 1
Nizhny Novgorod State Technical University N.a R.E. Alekseev, 24 Minin St, 603950 Nizhny Novgorod, Russia
2
Lobachevsky State University of Nizhni Novgorod-National Research University, 23 Prospect Gagarina (Gagarin Avenue), 603950 Nizhny Novgorod, Russia
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Polymer Bulletin
Introduction In recent years, amphiphilic vinyl polymers containing hydrophobic units and hydrophilic oligo(ethylene glycol) fragments have often been considered as components of promising biocompatible materials and new generation catalytic nanosystems [1–5]. The versatile way to introduce oligo(ethylene glycol) fragments into vinyl polymers of various compositions is radical copolymerization involving active monomers containing the specified fragments. Methoxy oligo(ethylene glycol) methacrylates (MOEGM) are unique amphiphilic macromonomers of this type, their copolymers being of great theoretical and practical interest in recent decades [6–10]. The presence of ethoxylated units in MOEGM molecules determines their hydrophilic-hydrophobic balance and surface-active properties [11, 12] and also affects su
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