Synthesis and characterization of ferrocene containing block copolymers

Abstract

Narrowly dispersed diblock copolymers containing poly(methyl methacrylate) [PMMA] or poly(nonafluorohexyl methacrylate) [PF9MA] as the first block and poly(ferrocenylmethyl methacrylate) [PFMMA] as the second block, were prepared by anionic polymerization for the first time. Disordered bulk morphologies in the case of PMMA-b-PFMMA were observed and explained in terms of low Flory-Huggins interaction parameter (v 0.04). In the case of PF9MA-b-PFMMA hexagonally packed cylinder morphology (HEX) was substantiated from TEM and SAXS observations. Furthermore, high incompatibility between PF9MA and PFMMA blocks allowed for the formation of well-ordered ferrocene containing cylinders on silica substrate upon exposure of the thin films to a saturated solvent vapor. It was shown that the cylinder orientation, parallel or perpendicular to the surface, could easily be controlled by appropriate choice of the solvent and without the need for preliminary surface modification, for example by means of grafted brush layer. V C 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 495-503 KEYWORDS: anionic polymerization; diblock copolymers; ferrocenylmethyl methacrylate (FMMA); Flory-Huggins interaction parameter; 1H,1H,2H,2H-nonafluorohexyl methacrylate (F9MA); order-disorder transition; rheology To the best of our knowledge, no well-ordered morphologies for PFMMA containing diblock copolymers were reported in the up-to-date literature. Resent work by Gallei et al. on poly (styrene) [PS] block copolymers with PFMMA (PS-b-PFMMA) Additional Supporting Information may be found in the online version of this article.

On the morphological behavior of ABC miktoarm stars containing poly(cis 1,4‐isoprene), poly(styrene), and poly(2‐vinylpyridine)

“…Rheological characterization was performed on a Rheometrics solids analyzer operated with a 0.5 mm shear gap sandwich configuration at 1% shear strain (γ) amplitude and 1 rad s −1 frequency (ω). All rheological data were obtained on heating the specimens from a disordered state under nitrogen flow to avoid sample degradation . For transmission electron microscopy (TEM) and small‐angle X‐ray scattering (SAXS) about 0.5 mm polymer films were produced by solvent casting from 7% THF solutions under nitrogen for 1 week in the dark followed by thermal annealing at 150, 175, or 200 °C for 5, 3, or 1 days, respectively, at ~0.001 mbar in the homebuilt vacuum chamber.…”

Recent Trends in Metallopolymer Design: Redox‐Controlled Surfaces, Porous Membranes, and Switchable Optical Materials Using Ferrocene‐Containing Polymers

“…[23][24][25][26] The latter approachl ead to welldefined poly(ferrocenyl methacrylate)-containing BCPs more recently. [27][28][29][30][31] Nuykena nd co-workers werea ble to polymerize VFc by meanso fa nionic polymerization to preparel ow molar mass BCPs with styrene,m ethyl methacrylatea nd propylene sulfide. [32] Some years later,t he anionic polymerization of VFc was carried out for BCPf ormation featuring higherm olar masses with poly(2-vinylpyridine) (P2VP), [33,34] poly(methyl methacrylate) (PMMA), [35] poly(ethylene oxide), [36,37] poly(N,N-dimethylaminoethyl methacrylate) [38] or poly(lactide) [39] as second block segment.…”

“…About twenty years later Pittman and co‐workers polymerized ferrocenyl (meth)acrylates by FRP as well as by anionic polymerization . The latter approach lead to well‐defined poly(ferrocenyl methacrylate)‐containing BCPs more recently . Nuyken and co‐workers were able to polymerize VFc by means of anionic polymerization to prepare low molar mass BCPs with styrene, methyl methacrylate and propylene sulfide .…”

On the properties of poly(isoprene-b-ferrocenylmethyl methacrylate) block copolymers

“…The temperature corresponding to the maximum rate of decomposition (T max ) is equal to 454 °C for PFMMA while for the diblock copolymers it is within the range 390-440 °C (Figure 1). Since upon decomposition PFMMA containing polymers in air will form pure Fe 2 O 3 as a residue [2], we could estimate the volume fractions (f PFMMA ) of PFMMA block from TGA data (see Table 1). The values obtained in such manner were averaged with NMR…”

“…Methacrylate derivatives of ferrocene have attracted scientific interest since 1970 due to their ability to undergo rapid free radical polymerization and their numerous technologically important properties which originate from the organometallic group [1][2][3]. Polymers bearing ferrocenyl groups are redox-active and therefore widely applied in the areas of electrochemical sensing, molecular recognition and energy storage [4][5][6].…”