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Spherical poly(ionic liquid) (PIL) nanoparticles of different size (25-70 nm) were synthesized and applied as a novel colloidal soft template for the preparation of meso- and macroporous inorganics, here exemplified with silica and its metal nanoparticle doping via nanocasting. Pore size and pore architecture can be adjusted by appropriate choice of the template and the reaction conditions. Unexpectedly, it was found that the in situ generated methanol plays a very important role during the casting process. It enlarged the overall surface area by introducing a significant fraction of micropores and small mesopores. The largest specific surface area was obtained at an optimized ratio of tetramethyl orthosilicate (TMOS) to PIL nanoparticle. In addition, PIL nanoparticles pre-functionalized with Pt metal nanoparticles were used in the same manner as hybrid templates for nanocasting. The pyrolysis conditions were optimized to synthesize mesoporous silica functionalized with uniformly distributed metal nanoparticles of very small size in a one-pot process. [ABSTRACT FROM AUTHOR]

Abstract: In recent years, polymeric/polymerized ionic liquids or poly(ionic liquid)s (PILs) were found to take an enabling role in some fields of polymer chemistry and material science. PILs combine the unique properties of ionic liquids with the flexibility and properties of macromolecular architectures and provide novel properties and functions that are of huge potential in a multitude of applications, including solid ionic conductor, powerful dispersant and stabilizer, absorbent, precursor for carbon materials, porous polymers, etc. So far, the preparation of PILs with various forms in cations and anions has mostly focused on the conventional free radical polymerization of IL monomers. Recent progress in the preparation of PILs via controlled/“living” radical polymerizations points out an unprecedented opportunity to precisely design and control macromolecular architecture of IL species on a meso-/nanoscale within a polymer matrix. There are also newly emerging polymerization techniques that have appeared for the preparation of PILs which have further pushed the limit of the design of PILs. In this review, we try to summarize the current preparative strategies of PILs, providing a systematic and actual view on the polymer chemistry behind. A discussion of the properties and applications of PILs constitutes the second part of this review. [Copyright &y& Elsevier]

Copolymers of 1,1-diphenylethylene (DPE) behave in a very special way in radical polymerization. Particularly, the behavior of MMA–DPE copolymers in radical polymerization is investigated. The results reveal that the semiquinoid structure of the precursor polymer identified in a previous contribution is activated by the attack of free radicals and thus, in a second stage polymerization with a second monomer, block copolymers are formed. The block copolymer yield depends strongly on the ratio between the amount of DPE-containing precursor polymer and the initiator and monomer concentration used in the second stage. The mechanism proposed is able to explain at least qualitatively all experimental results including the restriction of this mode of control of radical polymerization to the formation of diblock copolymers only. [Copyright &y& Elsevier]

An in-situ process for the grafting of a common poly(ionic liquid), poly(1-ethyl-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide), from natural cotton was developed. Unexpectedly and only found for this special morphology, the PIL coating even at a weight fraction as low as 3.4 wt%, could run accelerated activation of cotton into porous carbons at temperatures above 600 °C under nitrogen. During the activation process, good preservation of the microscopic fiber structure and the macroscopic morphology was achieved, and the resulting microporous carbons are mechanically highly flexible. Due to the special activation reaction of the PIL coating with the cotton, the as-formed microporous carbon is highly temperature and oxidation-stable and can be used for electrocatalytic reactions, here exemplified by the oxygen reduction reaction. This work thus points out a new, very simple pathway to process biomass with special architecture into functional porous carbons for electrochemical energy conversion. [ABSTRACT FROM AUTHOR]

Abstract: Different synthetic pathways have been explored to synthesize polysiloxane–acrylate and polysiloxane–urethane latexes with small and narrowly distributed particle sizes, using the specific advantages of the miniemulsion approach. Besides cross-linked latexes with high siloxane content, also hybrid particles were generated. [Copyright &y& Elsevier]

Abstract: Results on aqueous heterophase polymerization in the presence of either 1,1-diphenylethylene or water-soluble precursor polymers containing an α,p-dimer unit of 1,1-diphenylethylene are reported. The precursor polymers are bound covalently to the particles due to a special kind of chain transfer reaction showing on the one hand some features of controlled radical polymerization and leading on the other hand to the formation of block copolymers. Moreover, the covalently bound precursor molecules act as very efficient colloidal stabilizers of the final dispersion and thus, they can be considered as reactive surfactant with the additional ability to control radical polymerization (controlsurf). Under optimum conditions the precursor polymer molecules are almost completely covalently attached to polymer particles. Results are presented regarding block copolymer yields, solids content, and particle diameter in dependence on the polymerization conditions, particularly the precursor polymer concentration, the monomer as well as the initiator concentration, and the initiator type. Under optimum conditions the attainable block copolymer yields and the solids content of the final latexes can be above 95 and about 40%, respectively. Based on experimental results the mechanism of this special kind of controlled radical polymerization under the peculiarities of aqueous heterophase polymerization is discussed. [Copyright &y& Elsevier]

The role of 1,1-diphenylethylene (DPE) in radical emulsion polymerization of methyl methacrylate is investigated. The presence of DPE causes a strong decrease in both the rate of polymerization and the molecular weight. According to the results of structure analysis by means of MALDI-TOF mass spectrometry, UV–vis spectroscopy, and 1H–NMR spectroscopy, DPE is incorporated in the copolymer chain exclusively as a reactive recombinant α,p-dimer, underlining the peculiar role of DPE in radical polymerizations. [Copyright &y& Elsevier]

A non-ionic surfactant system is synthesized by standard grafting of poly(ethylene oxide) from renewable lignin fragments and used for the emulsion polymerization of styrene. The lignin precursors are formed by hydrogenolysis and utilized as initiator for the oxyanionic polymerization of ethylene oxide leading to amphiphilic polymers, very similar to standard nonionic surfactant synthesis. Subsequently, the formed amphiphilic polymers are employed as stabilizers in the heterophase polymerization of styrene with various initiators. Poly (styrene) latexes with solids contents of up to 21% depending on stabilizer concentration have been obtained. Stabilizer efficiencies and performances were nicely comparable with those of nonylphenol-based, non-ionic industrial performance surfactants. [ABSTRACT FROM AUTHOR]

In this work we studied covalently crosslinked poly(ionic liquid) nanoparticles synthesized via aqueous dispersion polymerization of 1,2,4-triazolium ionic liquid monomers in the presence of a dication crosslinker. Compared to their non-crosslinked counterparts, the nanoparticles showed improved structural integrity in organic media. Assisted by cryogenic electron microscopy, these nanoparticles were analyzed in detail and found to present vastly diverse shapes and highly ordered inner mesostructures. Upon altering the length of the alkyl substituents on the triazolium cation from dodecyl to tetradecyl and hexadecyl, a shape transformation from elongated “nanoworms” to a mixture of “onion-like” and “wasp-like” nanoparticles was observed. Additionally, the size variation of these colloidal nanoparticles was investigated systematically by polymerizations at different concentrations of monomer, external added salt and crosslinking agent. Finally, the crosslinked poly(ionic liquid) nanoparticles were able to readily disperse multi-walled carbon nanotubes in water and organic media. [ABSTRACT FROM AUTHOR]

Abstract: Nitrogen-doped carbon particles were produced using the hydrothermal carbonization of a nitrogen-containing carbohydrate, namely glucosamine, under mild temperature conditions (180 °C) followed by further calcination under a stream of inert gas at 750 °C. The resulting materials contain significant amounts of nitrogen doping within their structure, mainly as quaternary N involved in an aromatized/graphitized carbon structure according to X-ray photoelectron spectroscopy. This nitrogen-doped material was dispersed with nanolatexes having a high affinity for carbon. The resulting hybrid dispersions could be conveniently cast into dense and stable films for thermal and electrical conductivity measurements. The conductivities were commensurate with technical carbon nanotube latex-based films. A morphological analysis of the dispersing mechanism suggests that the potential for high performance materials realized in this contribution is very competitive, but still far from being fully exploited. [Copyright &y& Elsevier]

The solid-state structures of polystyrene–poly(Z-l-lysine) block copolymers were examined with respect to the polymer architecture and the secondary structure of the polypeptide using circular dichroism, quantitative small- and wide-angle X-ray scattering, and electron microscopy. Linear block copolymers exhibit a hexagonal-in-lamellar structure where folded and packed polypeptide α-helices form lamellae which extend over an exceptional broad range of the composition diagram. Star- or bottlebrush-shaped copolymers are able to stabilize a larger interface area than linear ones which promotes the formation of undulated lamellar mesophases. Depending on the secondary structure of polypeptide segments, plane lamellar, superundulated lamellar, or corrugated lamellar phases are formed. These results indicate the importance of a secondary structure and packing of polymer chains for the formation of new phases and ordering far from the ‘classical’ phase behavior. [Copyright &y& Elsevier]

Poly(ionic liquid) (PIL) integrates some intrinsic characteristics of ionic liquids (ILs) with classic merits of polymeric materials, and opens up a new dimension to research ionic polymers. Nanoporous PILs with controlled nanopores combine the advantages of two classes of functional materials, i.e., porous polymers and ILs, which greatly expand their applicability to energy storage and conversion, environmental sensing, gas sorption and catalysis. In this short review, we summarize the recent advances in the design and synthesis of nanoporous PILs, focusing on pore generation and engineering, electrostatic interactions, and potential applications to address energy and environmental issues. Porous carbons from nanoporous PIL templates/precursors are also briefly discussed as an extension of nanoporous PILs for energy research. Finally, our future perspectives on the potential of nanoporous PILs are presented. Image 1 • Nanoporous PIL has received wide interests in energy and environment fields. • Pores are introduced via template method, ionic complexation, post-treatment. • Nanoporous PIL can be converted into functional carbon nanomaterials. [ABSTRACT FROM AUTHOR]