We describe the synthesis and the solution properties of sheet- and disclike Janus particles, containing an inner crosslinked polybutadiene (PB) layer and two different outer sides of polystyrene (PS) and poly(tert-butyl methacrylate) (PtBMA). The structures formed upon adsorption of the flat Janus particles onto solid substrates as well as in THF solution are investigated. The Janus discs are obtained in a template-assisted synthetic pathway followed by sonication. Selectively crosslinking the lamellar PB domains in a well-ordered lamellar microphase-separated bulk morphology of PS-block-PB-block-PtBMA (SBT) block terpolymers leads to the conservation of the compartmentalization of the two outer blocks. Sonication of the crosslinked block terpolymer templates renders soluble sheet- and disclike Janus particles, the size of which can be tuned from the micrometer range down to the nanometer scale. Small-angle X-ray scattering, transmission electron microscopy, dynamic light scattering, scanning force microscopy, and scanning electron microscopy are used to characterize the template-assisted synthetic process and the solution properties. Cryogenic transmission electron microscopy in THF and TEM of particles, embedded into a photo-crosslinkable silicon oil, indicate a supramolecular aggregation behavior of the Janus discs in concentrated solutions. Pendant drop tensiometry demonstrates that Janus sheets and discs can be used to stabilize liquid−liquid interfaces, rendering these materials interesting for future applications.

The real time changes occurring within films of cylinder-forming poly(α-methylstyrene-block-4-hydroxystyrene) (PαMS-b-PHOST) were monitored as they were swollen in tetrahydrofuran (THF) and acetone solvent vapors. In situ information was obtained by combining grazing incidence small angle X-ray scattering (GISAXS) with film thickness monitoring of the solvent vapor swollen films. We show that for self assembly to occur, the polymer thin film must surpass a swollen thickness ratio of 212% of its original thickness when swollen in THF vapors and a ratio of 268% for acetone vapor annealing. As the polymer becomes plasticized by solvent vapor uptake, the polymer chains must become sufficiently mobile to self assemble, or reorganize, at room temperature. Using vapors of a solvent selective to one of the blocks, in our case PHOSTselective acetone, an order-order transition occured driven by the shift in volume fraction. The BCC spherical phase assumed in the highly swollen state can be quenched by rapid drying. Upon treatment with vapor of a non-selective solvent, THF, the film maintained the cylindrical morphology suggested by its dry-state volume fraction. In situ studies indicate that self-assembly occurs spontaneously upon attaining the threshold swelling ratios.

Summary: The bis‐hydrophilic block copolymer, poly(acrylic acid)45‐block‐poly(N,N‐diethylacrylamide)360, was obtained after hydrolysis of poly(tert‐butyl acrylate)45‐block‐poly(N,N‐diethylacrylamide)360, synthesized by sequential anionic polymerization of tert‐butyl acrylate (tBA) and N,N‐diethylacrylamide (DEAAm) in the presence of Et3Al. The polymer is stimuli‐sensitive with respect to both pH and temperature in aqueous solution, reversibly forming spherical crew‐cut micelles with PDEAAm‐core (〈Rh〉z = 21.5 nm) under alkaline conditions for T > 35 °C as well as inverse star‐like micelles with an expanded PAA‐core (〈Rh〉z = 43.8 nm) under acidic conditions for T < 35 °C, as indicated by dynamic light scattering.

Hyperbranched glycopolymers were synthesized by self-condensing vinyl copolymerization (SCVCP) of an acrylic AB* inimer, 2-(2-bromopropionyloxy)ethyl acrylate (BPEA), with 3-O-acryloyl-1,2:5,6-di-O-isopropylidene-α-d-glucofuranoside (AIGlc) via atom transfer radical polymerization (ATRP), followed by deprotection of the isopropylidene protecting groups. Homopolymerization of AIGlc with the CuBr/pentamethyldiethylenetriamine (PMDETA) catalyst system in solution resulted in linear poly(AIGlc) having controlled molecular weights and narrow molecular weight distribution, which were characterized using GPC, GPC/viscosity, and MALDI−TOF mass spectrometry. The catalyst system could be applied for SCVCP to synthesize hyperbranched poly(AIGlc)s, in which the molecular weights, the composition of AIGlc segment, and the branched structures can be adjusted by an appropriate choice of the comonomer ratio, γ. Deprotection of the isopropylidene protecting groups of the branched poly(AIGlc)s resulted in water-soluble glycopolymers with randomly branched architectures.