Exploiting the Site Selectivity of Perfluoropyridine for Facile Access to Densified Polyarylene Networks for Carbon-Rich Materials.

Fluorinated molecules containing reactive functionalities are of great interest to the materials community as these compounds can be used to prepare fluorinated polymers with desirable physical and electronic properties. Despite their potential, many of these compounds are limited by their synthesis which generally requires transition-metal-catalyzed coupling reactions or harsh fluorinating conditions. Perfluoroheteroaromatic compounds provide a unique solution to this problem as compounds such as perfluoropyridine can undergo SNAr reactions with a wide range of simple nucleophiles in a controlled and regioselective manner. Herein we report the transition-metal-free synthesis of a pool of highly soluble high aromatic content (HAC) perfluoropyridine-based thermosetting precursors and compounds of interest which can be easily obtained from readily available chemical precursors using simple nucleophilic chemistries. These thermally active monomers cure readily, in 350-400 °C temperature ranges, into highly densified polyaryelene networks and demonstrate decomposition temperatures well above 400 °C and high char yields at 900 °C, making these promising materials for high-temperature applications as well as templates for carbon-based nanomaterials.

Acid Exfoliation of Imine-linked Covalent Organic Frameworks Enables Solution Processing into Crystalline Thin Films.

Covalent organic frameworks (COFs) are highly modular porous crystalline polymers that are of interest for applications such as charge-storage devices, nanofiltration membranes, and optoelectronic devices. COFs are typically synthesized as microcrystalline powders, which limits their performance in these applications, and their limited solubility precludes large-scale processing into more useful morphologies and devices. We report a general, scalable method to exfoliate two-dimensional imine-linked COF powders by temporarily protonating their linkages. The resulting suspensions were cast into continuous crystalline COF films up to 10 cm in diameter, with thicknesses ranging from 50 nm to 20 µm depending on the suspension composition, concentration, and casting protocol. Furthermore, we demonstrate that the film fabrication process proceeds through a partial depolymerization/repolymerization mechanism, providing mechanically robust films that can be easily separated from their substrates.

Solvent-Assisted Desorption of 2,5-Lutidine from Polyurethane Films.

A fundamental understanding of chemical interactions and transport mechanisms that result from introducing multiple chemical species into a polymer plays a key role in the development and optimization of membranes, coatings, and decontamination formulations. In this study, we explore the solvent-assisted desorption of a penetrant (2,5-lutidine) in polyurethane with aprotic (acetonitrile) and protic (methanol) solvents. Chemical interactions between solvent, penetrant, and polymer functional groups are characterized via time-resolved Fourier transform infrared spectroscopy (FTIR) during single and multicomponent exposures. For both solvents, an increase in the extraction rate of the penetrant is observed when the solvent is applied during desorption. Inspection of the FTIR spectra reveals two potential mechanisms that facilitate the enhanced desorption rate: (1) penetrant/solvent competition for hydrogen donor groups on the polymer backbone and (2) disruption of the self-interaction (cohesive forces) between neighboring polymer chains. Finally, the aprotic solvent is found to generate an order of magnitude greater desorption rate of the penetrant, which is attributed to a greater disruption of the self-interaction during penetrant desorption compared to the protic solvent and the inability of an aprotic solvent to form larger and potentially slower penetrant-solvent complexes.

Synthesis and Characterization of Segmented Polyurethanes Containing Trisaminocyclopropenium Carbocations.

Diol-functionalized trisaminocyclopropenium (TACP) carbocations were used as chain extenders in a two-step synthesis of a segmented polyurethane. Differential scanning calorimetry demonstrated significant differences in the crystallization behavior of the poly(tetramethylene oxide) soft segment when minor changes were made to the TACP structure and when compared to a control that was chain extended with butane diol. Fourier transform infrared spectroscopy was used to characterize the different level of hydrogen bonding in the polymers and showed that the bulky, charged TACP chain extender limited hydrogen bonding interactions when compared to the control. Dynamic mechanical analysis was used to probe the thermomechanical behavior of polymers that showed that the TACP-containing polymers were much more resistant to flow at high temperatures when compared to the control. Small-angle X-ray scattering showed a phase separated morphology for all the polymers tested. Tensile testing of the TACP polyurethanes demonstrated an elastic response over a wide range of strain, followed by a significant strain hardening. These results suggest a morphology of ionic aggregates rather than hard segment physical cross-links.

Proximity field nanopatterning of azopolymer thin films.

A method for inscribing surface relief gratings in azopolymer thin films via proximity field nanopatterning is reported. Azopolymers prepared by ring opening metathesis polymerization were cast as thin films and brought into conformal contact with transparent polydimethylsiloxane phase masks. Irradiation of the film surface through the phase masks induces mass transport of azopolymer that generates surface relief structures on the basis of the intensity modulation of the light by structures on the phase mask. The experimental images obtained matched well with those produced by optical simulation. A wide variety of structures could be inscribed in the film surface which depended on the molecular weight of the azopolymer and irradiation time. Control experiments conducted suggest that the process is entirely photonic and that the presence of the phase mask on the film surface did not affect the inscription process.

Cationic comb polymer superdispersants for colloidal silica suspensions.

We investigate the ability of a cationic comb polymer composed of a poly(trimethylammonium iodide ethyl methacrylate) (PTMAM) backbone and uncharged poly(ethylene glycol) (PEG) teeth to stabilize aqueous silica suspensions of varying ionic strength and pH. Both PTMAM-g-PEG and its homopolymer backbone, PTMAM, are synthesized via reversible addition-fragmentation chain transfer followed by quaternization of the pendant amine groups with methyl iodide. Through a combination of polymer adsorption, zeta potential, and sedimentation measurements as well as confocal imaging of sediment structures, we find that PTMAM-g-PEG imparts stability over a broad range of solution conditions, where pure PTMAM fails.

Synthesis and aggregation behavior of thermally responsive star polymers.

To mimic the three-dimensional (3-D) globular architecture resulting from the precise positioning of hydrophobic/hydrophilic domains (blocks) of naturally occurring proteins, water-soluble linear and star homopolymers of N,N'-dimethylacrylamide (DMA) were synthesized with prescribed molecular weights via reversible addition-fragmentation chain transfer (RAFT) polymerization and subsequently used as macro chain transfer agents for block copolymerization with N-isopropylacrylamide (NIPAM). For the star block copolymers, the interior block consisted of NIPAM while the exterior block was DMA. Since polyNIPAM thermally switches from hydrophilic to hydrophobic, the 3-D solution conformations of the polymers were studied as a function of temperature using differential scanning calorimetry (DSC), static light scattering (SLS), and dynamic light scattering (DLS). The polymers were observed to form monodisperse aggregates in an aqueous pH 4 buffer solution when heated above the lower critical solution temperature (LCST) of polyNIPAM. The temperature at which the polymers aggregated and the size of the aggregates were dependent on the NIPAM block length and the core architecture. A simple model based on an optimal area per headgroup was used to analyze our experimental findings and was useful for predicting the final size and molecular weight of the aggregates formed.

Highly stereoselective Saucy-Marbet rearrangement using chiral ynamides. Synthesis of highly substituted chiral homoallenyl alcohols.

[reaction: see text] A highly stereoselective Saucy-Marbet rearrangement using chiral ynamides and propargyl alcohols is described here. This rearrangement can be catalyzed by para-nitrobenzenesulfonic acid leading to high diastereoselectivities for a range of different chiral propargyl alcohols and ynamides in a stereochemically intriguing matched, mismatched, or indifferent manner. This provides an excellent entry to highly substituted chiral homoallenyl alcohols.