Unimolecular Amphiphilic Nanocontainers Based on Dendronized Linear Polymers

Summary: Linear polymeric core, polyethylenimine (PEI), is successfully dendronized divergently using different‐generation polyamidoamine (PAMAM)‐type dendrons. The formed dendronized polymers are further end‐capped using long alkyl acrylate, hexyl acrylate, to give macromolecular amphiphiles, which perform as unimolecular nanocontainers, capable of encapsulating water‐soluble dye in their interiors. The encapsulation properties are found to be generation‐dependent, in which, at higher generations of nanocontainers, the cavity becomes more localized, due to dense packing of the dendrons at their termini.

Dendronization of a linear polymeric core followed by capping with hydrophobic arms.     

Tailoring Polymeric Hydrogels through Cyclodextrin Host–Guest Complexation

A close correllation between molecular‐level interactions and macroscopic characteristics of polymer networks exists. The characteristics of the polymeric hydrogels assembled from β‐cyclodextrin (β‐CD) and adamantyl (AD) substituted poly(acrylate)s can be tailored through selective host–guest complexation between β‐CD and AD substituents and their tethers. Dominantly, steric effects and competitive intra‐ and intermolecular host–guest complexation are found to control poly(acrylate) isomeric inter‐strand linkage in polymer network formation. This understanding of the factors involved in polymeric hydrogel formation points the way towards the construction of increasingly sophisticated biocompatible materials.

     

Fabrication of Superhydrophobic and Superoleophilic Polystyrene Surfaces by a Facile One‐Step Method

A facile one‐step method has been developed to prepare both superhydrophobic and superoleophilic surfaces of polystyrene (PS) without any chemical modification. A rough film consisting of micro‐bead and nano‐fiber mixed structures is formed by spraying a PS solution onto a large area and any type of substrate. The mixed structures with such unique wettability properties can be used in oil/water separation and as oil sorbents.

     

Synthesis of Thermosensitive PNIPAM‐co‐MBAA Nanotubes by Atom Transfer Radical Polymerization within a Porous Membrane

Summary: Thermosensitive polymer nanotubes can be fabricated within an aminopropylsilane‐modified porous anodic aluminum oxide membrane by surface‐initiated atom transfer radical polymerization (ATRP) followed by template removal. DSC experiments prove that the synthesized PNIPAM‐co‐MBAA copolymer nanotubes have a reversible thermosensitive behavior. The temperature‐induced changes in dimension and shape of the nanotubes were studied by AFM in real time in an aqueous environment. It indicates that the nanotubes undergo a shape alteration from an “ellipse” to “circular” shape in water upon heating to LCST or above.

DSC curves of PNIPAM‐co‐MBAA nanotubes.     

RAFT Inverse Miniemulsion Polymerization of Acrylamide

RAFT inverse miniemulsion polymerization is demonstrated for the first time as an alternate way to synthesize hydrophilic polymer latexes. The kinetic behavior of inverse RAFT miniemulsion polymerization of acrylamide is similar to that observed in aqueous RAFT solution polymerization. A water‐soluble initiator provides better control than a lipophilic initiator in inverse RAFT miniemulsion polymerization under the conditions used here.

     

Tandem RAFT Polymerization and Click Chemistry: An Efficient Approach to Surface Modification

PS grafted silica nanoparticles have been prepared by a tandem process that simultaneously employs RAFT polymerization and click chemistry. In a single pot procedure, azide‐modified silica, an alkyne functionalized RAFT agent and styrene are combined to produce the desired product. As deduced by thermal gravimetric and elemental analysis, the grafting density of PS on the silica in the tandem process is intermediate between analogous “grafting to” and “grafting from” techniques for preparing PS brushes on silica. Relative rates of RAFT polymerization and click reaction can be altered to control grafting density.

     

Synthesis of Conjugated Polymer Nanoparticles in Non‐Aqueous Emulsions

Summary: A novel non‐aqueous emulsion system, consisting of cyclohexane as the continuous and acetonitrile as the dispersed phase, is described. Stabilization of the system can be achieved by using polyisoprene‐block‐poly(methyl methacrylate) copolymers as emulsifiers. The suitability of this system for performing water‐sensitive, catalytic, and oxidative polymerizations and polycondensations is demonstrated by the synthesis of poly(3,4‐ethylenedioxythiophene), poly(thiophene‐3‐yl‐acetic acid), and polyacetylene. In all cases spherical nanoparticles with diameters as small as 23 nm can be obtained.

     

Potentials and Limitations of Automated Parallel Emulsion Polymerization

The application of automated parallel synthesizer robots for the investigation of polymerization processes is of major interest at present. In this contribution we describe the application of the emulsion polymerization of styrene and vinyl acetate. The preparations of emulsions and latexes were investigated in detail and compared to “conventional” stirred tank reactors. In particular the influence of the vortex mixing as well as the limitations regarding solid content and reactor fouling are addressed.

     

Investigating the Molecular Architecture of Hyperbranched Polymers

Hyperbranched polymers constitute a unique class of branched macromolecules, where structural complexity is complemented by relative ease of synthesis. The increasing interest in the study of these materials is due to their distinctive properties, inherently tied to their complex molecular architecture, and is augmented by the continual growth of applications like catalysis, viscosity modifiers, and sensors. We report a structural model for HBPs based on fractal scaling of both mass and connectivity. This model is shown to be of use in understanding small angle scattering data, especially in comparison with nuclear magnetic resonance spectroscopy for structural characterization.

     

Self‐Organizing Alignment of Carbon Nanotubes in Thermoplastic Polyurethane

Summary: A simple compounding technique for the fabrication of polymer nanocomposites with single‐walled carbon nanotubes having exceptional alignment and improved mechanical properties is described. The aligned‐nanotube composite was prepared by dissolving single‐walled carbon nanotubes in a solution of thermoplastic polyurethane and tetrahydrofuran. Solvent‐polymer interactions that induce the orientation of soft chain segments during the swelling and moisture curing stage are believed to serve as a driving force for the macroscopic alignment of the carbon nanotubes.

Alignment of single‐walled carbon nanotubes in thermoplastic polyurethane during polar solvent exposure.     

Supramolecular Hydrogels with CdS Quantum Dots Incorporated by Host–Guest Interactions

In this communication, β‐cyclodextrin modified quantum dots were used as a water‐soluble “supramolecular” cross‐linker (SCL) because of its surface's supramolecular activity. The guest monomer‐loaded SCL (mSCL) can be used to copolymerize with water‐soluble monomers leading to transparent hybrid supramolecular hydrogels. This simple and versatile method opens new venues for the preparation of hybrid supramolecular hydrogels and the host–guest chemistry of cyclodextrins.

     

Micellization Phenomena in Semicrystalline Block Copolymers: Reflexive and Critical Views on the Formation of Cylindrical Micelles

Investigations on the self‐assembly of block copolymers in solution have in some way a less well‐studied history than the study of their phase separation in the solid state, and many aspects are yet not completely understood. Here we focus on the behavior of a specific class of copolymers, namely semicrystalline block copolymers, capable of forming cylindrical aggregates in a solvent selective for the non‐crystalline, complementary block. A common model of micellization is proposed, in principle applicable to most of these copolymeric systems.

     

Crosslinkable Composite Spheres and Capsules Synthesized by Heterocoagulation

Summary: Crosslinkable composite microspheres were prepared by heterocoagulation of epoxy resin nanoparticles onto polystyrene microspheres. The corresponding hollow microspheres were created after removal of the core. The surface morphology was tunable from smooth to rough by controlling the degree of crosslinking of the shell nanoparticles. A positively charged polyelectrolyte could be easily adsorbed onto the composite microspheres to facilitate further synthesis, e.g., layer‐by‐layer deposition and a sol‐gel process to form inorganic materials.

An SEM image of the PS/EP/silica (where the EP was crosslinked slowly) microspheres after the cores have been removed.     

Preparation of a Polyethylene Latex by Catalytic Hydrogenation of a Polybuta‐1,4‐diene‐Based Dispersion

Summary: Fully linear polyethylene‐based latexes have been prepared by the hydrogenation of polybuta‐1,4‐diene dispersions. The latter were synthesized via dispersion ring‐opening metathesis polymerization of cycloocta‐1,5‐diene, and hydrogenated using RuCl₂(PPh₃)₃ as catalyst, without any further treatment. A high hydrogenation efficiency was achieved as demonstrated by different techniques including DSC, and ¹H NMR and FT‐IR spectroscopy. The hydrogenation process could be carried out without detrimental effect on particle size and colloidal stability as evidenced by optical microscopy and light scattering analysis.

Optical microscopy photograph of a polybutadiene‐based dispersion after hydrogenation. No change in size is observed.