Templating porosity in polymethylsilsesquioxane coatings using trimethylsilylated hyperbranched polymers

A series of trimethylsilyl end-functionalized aliphatic hyperbranched polymers has been used to template porosity in polymethylsilsesquioxane films prepared by heat treatment of a spin cast methylsilsesquioxane precursor. By varying the extent of the end-functionalization, closed pore foams with controlled pore sizes and pore contents of up to 40 vol% were obtained by chemically-induced phase separation and thermal degradation of the hyperbranched polymers during the heat treatmen

Synthesis of fluorinated alkoxyamines and alkoxyamine-initiated nitroxide-mediated precipitation polymerizations of styrene in supercritical carbon dioxide

TIPNO (2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitroxide)-alkoxyamine was found to give reasonably controlled/living nitroxide-mediated (NMP) precipitation polymerizations of styrene in supercritical carbon dioxide (scCO(2)). In contrast under the same conditions, the analogous SG1 (N-tert-butyl-N-(1-diethylphosphono-2,2-dimethylpropyl)nitroxide)-alkoxyamine gave higher rates of polymerization and inferior controlled/living character. The circumvention of the requirement for excess free (nitroxide](0) allowed the study of nitroxide partitioning effects in scCO(2) for three newly synthesized fluorinated alkoxyamines. Two alkoxyamines dissociated into scCO(2)-philic fluorinated TIPNO-nitroxide derivatives, while another contains a similar sized fluorinated "foot". Despite the increased steric bulk about the N-O bond for the novel fluorinated alkoxyamines, all polymerizations proceeded at a similar rate and level of control to the TIPNO system in solution (toluene). PREDICI simulations for the styrene/TIPNO system are used to support extensive partitioning effects observed in scCO(2) for the fluorinated alkoxyamines.Irish Research Council (formerly IRCSET) IUPAC Transnational Call in Polymer Chemistry to F.Aldabbagh. National Science Foundation (NSF CHE-1057927, USA) to R. Braslau.peer-reviewe

Industrially-relevant polymerization-induced self-assembly formulations in non-polar solvents: RAFT dispersion polymerization of benzyl methacrylate

Industrially-sourced mineral oil and a poly(α-olefin) are used as solvents for the reversible addition–fragmentation chain transfer (RAFT) dispersion polymerization of benzyl methacrylate (BzMA) using a poly(lauryl methacrylate) macromolecular chain transfer agent (PLMA macro-CTA) at 90 °C. The insolubility of the growing PBzMA chains under such conditions leads to polymerization-induced self-assembly (PISA), whereby poly(lauryl methacrylate)-poly(benzyl methacrylate) (PLMA-PBzMA) diblock copolymer spheres, worms or vesicles are produced directly as concentrated dispersions. The particular diblock copolymer composition required to access each individual morphology depends on the nature of the oil. Moreover, the solvent type also affects important properties of the physical free-standing gels that are formed by the PLMA-PBzMA worm dispersions, including the storage modulus (G′), critical gelation temperature (CGT) and critical gelation concentration (CGC). Spherical PLMA-PBzMA diblock copolymer nanoparticles can be prepared at up to 50% w/w solids and an efficient ‘one-pot’ protocol involving solution polymerization of LMA followed immediately by dispersion polymerization of BzMA has been developed. The latter formulation enables high BzMA conversions to be achieved, with spherical nanoparticles being produced at 30% w/w solids

Asymmetric copolymers: synthesis, properties, and applications of gradient and other partially segregated copolymers

This is an accepted manuscript of an article published by Wiley in Macromolecular Rapid Communications, available online: https://doi.org/10.1002/marc.201800357 The accepted version of the publication may differ from the final published version.Asymmetric copolymers are a class of materials with intriguing properties. They can be defined by a distribution of monomers within the polymer chain that is neither strictly segregated, as in the case of block copolymers, nor evenly distributed throughout each chain, as in the case of statistical copolymers. This definition includes gradient copolymers as well as block copolymers that contain segments of statistical copolymer. In this review, different methods to synthesize asymmetric copolymers are first discussed. The properties of asymmetric copolymers are investigated in comparison to those of block and random counterparts of similar composition. Finally, some examples of applications of asymmetric copolymers, both academic and industrial, are demonstrated. The aim of this review is to provide a perspective on the design and synthesis of asymmetric copolymers with useful applications.This research was financially supported by the ASYMCOPO Project, an international collaborative research project of the Deutsche Forschungsgemeinschaft (DFG, Germany) and the Agence Nationale de la Recherche (ANR, France); DFG project: GU 1685/1-1 (J. Z., C. G. S. and U. S. S.) and ANR project ANR-15-CE08-0039 (S. H.). C. G. S. and U. S. S. thank the Center for Excellence “PolyTarget” (SFB 1278, project Z01) of the Deutsche Forschungsgemeinschaft (DFG, Germany) for financial support. B. F. M. acknowledges the financial support from Consejo Nacional de Ciencia y Tecnologia (CONACyT, Mexico) to pursue her PhD.Published versio