Preparation of polyhedral oligomeric silsesquioxane‐containing block copolymer with well‐controlled stereoregularity

Abstract

Preparation of functional domains with a spacing of 10 nm is a benchmark set to fabricate next‐generation electronic devices. Organic–inorganic block copolymers form well‐ordered microphase separations with very small domain sizes. The design and preparation of a novel block copolymer consisting of syndiotactic polymethyl methacrylate (st‐PMMA) and polyhedral oligomeric silsesquioxane (POSS)‐functionalized polymethacrylate, designated as st‐PMMA‐b‐PMAPOSS, which can recognize functional molecules, are reported. The st‐PMMA segments form a helical structure and encapsulate C60 in the helical nanocavity, leading to the formation of an inclusion complex. Although the ordering of the domains is not high, C60 domains that are in a quasi‐equilibrium state, with about 10‐nm domain spacings, are generated using st‐PMMA‐b‐PMAPOSS that can recognize functional molecules. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2181–2189

Preferred‐handed helical conformation in organic–inorganic hybrid block copolymers with well‐controlled stereoregularity

“…The conventional poly(styrene‐ b ‐methyl methacrylate) is difficult to obtain domain spacing of less than 24 nm because Flory‐Huggins interaction parameter, χ , is not enough 22 . On the other hand, organic–inorganic hybrid block copolymer: at ‐PMMA‐ b ‐PMAPOSS could achieve the formation of domain spacing of 12 nm 8b . If this notion can be simply converted to an it ‐PMAPOSS‐ b ‐PMMA, strong repulsions between it ‐PMAPOSS and it ‐PMMA could take place.…”

“…Various kinds of block copolymers containing‐POSS such as poly(styrene‐ b ‐PMAPOSS) (PS‐ b ‐PMAPOSS), 5 poly(ethylene oxide‐ b ‐PMAPOSS) (PEO‐ b ‐PMAPOSS), 6 and poly(trifluoroethyl methacrylate‐ b ‐PMAPOSS) (PTFEMA‐ b ‐PMAPOSS) were also prepared 7 . A previous study has reported the synthesis of PMMA‐ b ‐PMAPOSS, which exhibited a well‐ordered microphase separation with a minimum domain spacing of 12 nm 1c,8 …”

Nitroxide‐mediated radical polymerization of methacryloisobutyl POSS and its block copolymers with poly(n‐acryloylmorpholine)

“…The so‐called reversible deactivation radical polymerization (RDRP) and living anionic polymerization are the powerful synthetic tools that have been successfully employed to achieve well‐defined POSS based hybrid (co)polymers of different composition and topologies . As an example, Hirai et al successfully polymerized POSS‐MA up to a degree of polymerization (DP) = 29 with a dispersity Ð –1.04 by living anionic polymerization that was successfully chain extended with styrene (S) and methyl methacrylate (MMA), subsequently affording well‐defined block copolymers, which could self‐assemble into hierarchical nanostructures .…”

Controlling Circularly Polarized Luminescence Using Helically Structured Chiral Silica as a Nanosized Fused Quartz Cell

“…The number-average molecular weight (M n ) and polydispersity index (Đ) were 8000 and 1.24, respectively. The stereoregularity of it-PMAPOSS was evaluated by using 13 C NMR spectroscopy. The signals at ∼45 ppm were assigned to meso− meso (mm), meso−racemo (mr), and racemo−racemo (rr) couplings from low to high magnetic field values, respectively.…”