A novel process to produce a nanochannel comprised of a void in a polymer matrix is reported. The processing involves a selective degradation of one of the bicontinuous microdomain phases of microphase-separated block copolymers to create a continuous, tortuous hole having a diameter of nanometer scale (nanochannel) and plating of the surfaces with nickel metal. The nanochannel and the metal plating were confirmed by the transmission and scanning electron microscopies.

A study of the radical polymerization of styrene macromonomers having a methacryloyl end group (MA-PSt; Aí" = 4400,12 400) and a vinylbenzyl end group (VB-PSt; Aí" = 4980,13 200) was carried out by using gel permeation chromatography with a laser light scattering detector (LS-GPC) and electron spin resonance spectroscopy (ESR). It was shown that the degree of polymerization of poly(macromonomer)s (Dp) measured by LS-GPC drastically varied with the macromonomer concentration in the feed ([M]); however, there was little difference in the Dp versus [M] curves between MA-PSt and VB-PSt of the same molecular weight. The Dp of poly(macromonomer)s was small (typically less than 10) at low [M] and increased rapidly with an increase in [M] followed by the sudden decrease to Dp = 1 at very high [M], The Dp versus [M] relationship was strongly affected by the molecular weight (Mw) of the macromonomers. These Dp versus[M] relationships were quite similar to Dp (or Rp) versus the degree of conversion relationship of the polymerization system of conventional small monomers in the presence of the gel effect. This indicated that the diffusion-controlled effect in macromonomer systems could be clearly described by [M] and Mv of the macromonomer.It was also shown that time-conversion curves of these macromonomers were monotonic and exhibited no feature of the autoacceleration effect normally observed in the polymerization system of small monomers in the presence of the gel effect. In addition, the polymerization rate (Rp) of MA-PSt was considerably greater than that of VB-PSt of the same molecular weight. ESR spectra of the propagating radical of MA-PSt and VB-PSt were measured to evaluate the concentration of the propagating radicals.From the results of ESR and LS-GPC, the propagation rate constant kp, the termination rate constant kt, and the radical lifetime rp of the macromonomers are evaluated and discussed.

Fine palladium (Pd) particles, which have a diameter of 4−5 nm and are coordinated with the poly(2-vinylpyridine) homopolymer (P2VP) or poly(2-vinylpyridine)-block-polyisoprene diblock copolymer (P2VP-b-PI), were prepared by the reduction of palladium acetylacetonate (PdII(acac)2) with 1-propanol in the dilute benzene solution of P2VP or P2VP-b-PI. These Pd “nanoparticles” were selectively incorporated into a particular region of microdomains by casting a solution comprised of the Pd nanoparticles, P2VP-b-PI, and chloroform as a solvent into film specimens. The nanoparticles coordinated with P2VP were selectively incorporated into the P2VP domains, while those coordinated with P2VP-b-PI were around the interface between the P2VP and PI domains.