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The vinyl addition polymerization of norbornyl-based monomers bearing polar functional groups is often problematic, leading to low molecular weight polymers in poor yield. Herein, we provide proof-of-principle evidence that addition-type homopolymers of siloxane substituted norbornyl-based monomers may be readily synthesized using the catalyst trans -[Ni(C 6 F 5 ) 2 (SbPh 3 ) 2 ]. Polymerizations using this catalyst reached moderate to high conversion in just 5 min of polymerization and produced siloxane-substituted polymers with molecular weights exceeding 100 kg/mol. These polymers showed excellent thermal stability ( T d ≥ 362 °C) and were cast into membranes that displayed high CO 2 permeability and enhanced CO 2 /N 2 selectivity as compared to related materials.

A water-soluble poly[( m -phenylenevinylene)- alt -( p -phenylenevinylene)] (PmPV) 2 has been synthesized, which exhibits an unsymmetrical substitution pattern on the para -phenylene unit. With one substituent being hydrophilic while the other being hydrophobic, the polymer chain has a higher tendency to fold in aqueous solution, thereby promoting helical conformation. The polymer is found to selectively disperse the single-walled nanotubes (SWNTs) of small diameters ( d = 0.75-0.84 nm), in sharp contrast to PmPV 1 with a symmetrical substitution pattern. The intriguing diameter-based selectivity is believed to be associated with the confined helical conformation, which provides a suitable cavity to host the SWNT of proper sizes. The study thus provides a useful demonstration that the polymer conformation can have a profound impact on the SWNT sorting.

Electronic and mechanic properties of single-walled carbon nanotubes (SWNTs) are uniquely dependent on the tube's chiralities and diameters. Isolation of different type SWNTs remains one of the fundamental and challenging issues in nanotube science. Herein, we demonstrate that SWNTs can be effectively enriched to a narrow diameter range by sequential treatment of the HiPco sample with nitric acid and a π-conjugated copolymer poly(phenyleneethynylene) (PPE)- co -poly(phenylenevinylene) (PPV). On the basis of Raman, fluorescence, and microscopic evidence, the nitric acid is found to selectively remove the SWNTs of small diameter. The polymer not only effectively dispersed carbon nanotubes but also exhibited a good selectivity toward a few SWNTs. The reported approach thus offers a new methodology to isolate SWNTs, which has the potential to operate in a relatively large scale.