An ESR Spin-Label Study on Molecular Mobility in the Interface between Microphases of a Diblock Copolymer: Effects of Admixture of Homopolymers That Are Miscible with One of the Blocks

Abstract

Molecular mobility in the interfacial region of a microphase-separated structure was studied in binary mixtures of AB-type diblock copolymers and homopolymers (miscible with only A) by the spin-label technique. In this study, we prepared (a) binary blends of polystyrene-block-poly(methyl acrylate) (PS-block-PMA) and homopolymer poly(cyclohexyl acrylate)'s having the number-averaged molecular weight (Mn) of 1000 (PCHA-S) and (b) having the Mn of 17300 (PCHA-L), and (c) binary mixtures of the PS-block-PMA and homopolymer PS with the Mn of 900 (PS-1). Emphasis was placed on effects of the molecular weight and the miscibility of added homopolymers on the mobility in the interfacial region of the microphase separation. Selective incorporation of the added PCHA-S, PCHA-L, and PS-1 into the PS phase of the PS-block-PMA was confirmed by modulated-temperature differential scanning calorimetry (MDSC) measurement as a decrease in the glass transition temperature of the PS phase. Moreover, the MDSC and small-angle X-ray scattering (SAXS) measurements suggested that the spatial distributions of the PCHA-S and PS-1 in the PS phase were relatively uniform because of their small Mn. On the other hand, the distribution of the PCHA-L in the PS phase was somewhat heterogeneous because of the large Mn of the PCHA-L. The spin-label at the junction point of the PS-block-PMA allowed us to estimate the mobility in the interfacial region of the microphase separation. Influence of the PCHA-S and PCHA-L on the mobility in the interfacial region was negligible even though the relatively uniform distribution of the PCHA-S in the PS phase was suggested by the SAXS and MDSC. More uniform distribution of the PS-1 than that of the PCHA-S in the PS phase was suggested by the SAXS, and the mobility in the interfacial region was slightly enhanced by the addition of the PS-1. However, the mobility was almost constant against an increase in the PS-1. The PS-1 was considered to be penetrated into the interfacial region and activated the mobility, but the fraction of the PS-1 in the interfacial region was constant irrespective of the blended amount of the PS-1. These results suggest that effects of homopolymers on the mobility in the interface are significantly related to their spatial distribution in the host phase.