Defined Poly[styrene‐block‐(ferrocenylmethyl methacrylate)] Diblock Copolymers via Living Anionic Polymerization

Abstract

Ferrocenylmethyl methacrylate (FMMA) is one of the very few metallocene-based monomers that are promising candidates for truly living anionic polymerization. Nevertheless, FMMA homopolymers with a narrow polydispersity, or block copolymerization studies that result in satisfying blocking efficiencies, are unknown so far. Here we describe a procedure that leads to highly regular FMMA-based polymers for the first time, characterized by polydispersity indices (PDI) of less that 1.05 and very high blocking efficiencies (>95%) in sequential copolymerization with styrene. Some of the obtained poly[styrene-block-(ferrocenylmethyl methacrylate)]s show unusual microphase morphologies, presumably the consequence of high T(g) s causing 'frustrated' non-equilibrium states.

Silacyclobutane‐Based Diblock Copolymers with Vinylferrocene, Ferrocenylmethyl Methacrylate, and [1]Dimethylsilaferrocenophane

“…THF, n‐ hexane, and LiCl were dried and deoxygenated following standard procedures. FS 1 ,34–39 FMMA 3 ,20 and vinylferrocene (VFc) 5 23 were synthesized and purified as reported elsewhere. n ‐BuLi (1.6 M solution in n ‐hexane) was used as the initiator for anionic chain growth.…”

“…All syntheses were carried out under an atmosphere of nitrogen or argon using the Schlenk technique or a glove‐box equipped with a Coldwell apparatus. Characterization methods were as reported recently20, 21, 23 and specified in the Supporting Information.…”

“…Manners' anionic polymerization of ansa ‐metallocenophanes13–15 1 → 2 is one of the established examples, and anionic polymerization of ferrocenylmethyl methacrylate (FMMA) 3 → 4 is another one. The latter approach was first described by Pittman et al in the early 1970s,16–19 but could only be developed into a truly living methodology by us very recently 20, 21. Even more recently, we could show that Nuyken's22 anionic polymerization of vinylferrocene (VFc) 5 → 6 , which usually suffers from severe limitations, performs a truly living methodology under specific conditions as well 23…”

Anionic Polymerization: Recent Advances

“…The formation of fascinating Janus micelles by ABC block terpolymers, PS-b-PB-b-PMMA, was reported [207]. Examples of typical functional block copolymers composed of PS block(s) that have been synthesized include: PS-b-PEO, PS-b-P(2VP); PS-b-PHEMA [210]; PS-b-poly(2,3-dihydroxypropyl methacrylate) [108,109]; PS-b-poly(2-dialkylaminoethyl methacrylate) (A. Hirao and T. Watanabe, unpublished results); PS-b-poly(oligo(ethylene glycol) methacrylate) [115][116][117][118]120]; PS-b-poly(lactide) [211]; PS-b-poly(ε-caprolactone); PS-b-poly(2-(perfluorooctyl)ethyl methacrylate) [212]; PS-b-poly(6-(4-(4-methoxyphenyl)phenoxy)hexyl methacrylate) [103]; PS-b-poly(3-(trialkoxysilyl)propyl methacrylate) [113]; PS-b-poly(ferrocenylmethyl methacrylate) [102]; PS-b-poly(ferrocenyldimethylsilane) [213]; and PS-b-poly(polyhedral oligomeric silsesquioxane (POSS) methacrylate) [97]. Consequently, the hierarchy of molecular organization, passing from supramolecular assemblies to nanodevices, has been recognized as being a very important issue in nanoscience and technology.…”

Side chain effects in the packing structure and stiffness of redox-responsive ferrocene-containing polymer brushes

“…Vancso et al [18][19][20][21] showed that PFS polymer/polymer brushes can be used as a so-called smart material in applications ranging from chemical sensors, smart membranes, to actuators. http Alternatively, the Fc moieties are tethered to the polymer backbone with a linker rather than integrated in the backbone, such as poly(vinylferrocene) (PVF) [22][23][24], poly(ferrocenylethylene) [25], and ferrocene-containing acrylates or methacrylates [26][27][28][29][30][31][32][33]. Hardy et al [34] reported the synthesis of side chain Fc-containing methacrylate polymers obtained by atom transfer radical polymerization (ATRP) and measured the thermal and redox properties of these polymers.…”