Assembly Structure Formation in Bulk and Ultrathin Films of Poly(substituted methylene) Having an Azobenzene Side Chain.

The density of the side chain introduced to a polymer main chain greatly influences the properties and functions of the polymer. This work first reports on the packing structure and properties at an interface of a poly(substituted methylene) where an azobenzene side chain is introduced at every carbon atom in the main chain (C1PAz). The structure and properties are compared with those of a conventional vinyl polymer [poly(methacrylate)] possessing an identical side-chain structure (C2PAz). The packing structure in the bulk state analyzed by X-ray measurements revealed that C1PAz adopts a highly ordered rectangular unit cell structure, whereas C2PAz shows a less ordered lamellar one. Langmuir film balance experiments indicated that both polymers with the trans-azobenzene give essentially the identical 2D side-chain occupying area on water, which agrees well with the smectic B (hexatic packing) model based on the X-ray data. Upon transfer onto a solid substrate, only C1PAz shows a conformational transformation to a spread bilayer-type layer, most probably due to conformational frustration stemming from the crowding of the side chains. This study proposes new insights into the effects of side-chain density on the self-assembly and photoreaction of azobenzene-containing polymers, which are expected to expand the possibilities of polymer design for various applications.

Single-Component Polycondensation of Bis(alkoxycarbonyldiazomethyl)aromatic Compounds To Afford Poly(arylene vinylene)s with an Alkoxycarbonyl Group on Each Vinylene Carbon Atom.

The original synthetic strategy for a new type of poly(arylene vinylene) (PAV) is presented, where the C=C-bond-forming coupling of bis(alkoxycarbonyldiazomethyl)aromatic compounds is utilized as propagation. The strategy is unique in that the resulting PAVs have an alkoxycarbonyl group as an electron-withdrawing substituent on each vinylene carbon atom in the polymer main chain. Among the transition-metal catalysts examined in this study, RuCl(cod)Cp* (cod = 1,5-cyclooctadiene, Cp* = pentamethylcyclopentadienyl) is the most efficient, affording PAVs from a series of bis(alkoxycarbonyldiazomethyl)aromatic compounds with a high trans-C=C-forming selectivity of up to 90%. A PAV sample with a fluorenylene framework as an arylene moiety prepared by the Ru catalyst exhibited a hole mobility of 4 × 10-6 cm2 V-1 s-1.

Self-Assembly of Hierarchical Structures Using Cyclotriphosphazene-Containing Poly(substituted methylene) Block Copolymers.

The cyclotriphosphazene-substituted diazoacetate homopolymer (polyPNDA') (PNDA' = hexaphenoxy-substituted phosphazene-containing methylene) and a novel poly(substituted methylene) block copolymer, polyPNDA'-block-poly(hexyloxycarbonylmethylene) (polyPNDA'-b-polyHDA'), were synthesized, and the self-assembly behavior of these polymers was studied in detail. A hexagonally packed aggregated structure was observed in the self-assembled structure of polyPNDA', whereas a lamellar structure was observed in the microphase-separated nanoassembly of polyPNDA'-b-polyHDA'. These results indicate that a hierarchical structure composed of highly regular polyPNDA' nanoaggregates and the long-range microphase-separated polyPNDA' and polyHDA' domains had formed.

Dispersion polymerization of styrene using a polystyrene/poly(L-glutamic acid) block copolymer as a stabilizer.

A block copolymer (PS-b-poly(L-Glu)) composed of polystyrene and poly(l-glutamic acid) was used as a stabilizer for dispersion polymerization of styrene. When dispersion polymerization of styrene was conducted at 70°C in 80% dimethylformamide-water with 0.5 wt% PS-b-poly(L-Glu), spherical polystyrene particles with D(n)=0.72 µm and narrow size distribution were obtained. Whereas AIBN concentration did not have any effects on particle size, molecular weight of the polystyrene particles was strongly dependent on the initiator concentration. As concentration of the PS-b-poly(L-Glu) increased from 0.2 to 1.0 wt%, particle size decreased from D(n)=0.91 to 0.69 µm with keeping surface area occupied by one poly(L-glutamic acid) chain about S=50 nm(2). On the other hand, an increase in initial concentration of styrene from 2 to 20 wt% caused an increase in particle size from D(n)=0.48 to 1.36 µm and a decrease in surface area per poly(L-glutamic acid) block from S=91 to 45 nm(2). Colloidal stability of the polystyrene particles in aqueous solution was responsive to pH due to the surface-grafted poly(L-glutamic acid). For dispersion polymerization of styrene, the PS-b-poly(L-Glu) functions as both a stabilizer and a surface modifier.

Effects of polystyrene-b-poly(aminomethyl styrene)s as stabilizers on dispersion polymerization of styrene in alcoholic media.

The effects of polystyrene-b-poly(aminomethyl styrene) (PS(n)-b-PAMS(m)) stabilizers on the particle size (D(n)) and size distribution (PSD) in dispersion polymerization of styrene were investigated. The block copolymers, PS(n)-b-PAMS(m), were prepared as follows: (i) atom transfer radical polymerization (ATRP) of styrene (PS-Br), (ii) ATRP of vinylbenzylphthalimide with the PS-Br (PS-b-PVBP), and (iii) treatment of the PS-b-PVBP with hydrazine. When the dispersion polymerization of styrene proceeded at 60 degrees C in ethanol with PS(19)-b-PAMS(130) stabilizer, spherical polystyrene particles with D(n)=0.91 microm (PSD=1.01) were obtained. The particle size was strongly affected by the copolymer composition. With an increase in PAMS block length from m=54 to 100 in PS(17)-b-PAMS(m), particle diameter became smaller from 1.55 to 0.91 microm. On the other hand, an increase in the length from m=20 to 82 in PS(34)-b-PAMS(m)s caused an increase in particle size from 0.35 to 0.70 microm. Titration of the particles suggests that 14-81% of stabilizers used in the polymerization system were attached on the polystyrene particle surfaces, depending on the composition of the block copolymers. Thus, for the dispersion polymerization of styrene, PS(n)-b-PAMS(m) block copolymers have both functions as a stabilizer during polymerization and surface-modification sites of polystyrene particles.