Organic–inorganic poly(N‐vinylpyrrolidone) copolymers with double‐decker silsesquioxane in the main chains: Synthesis, glass transition, and self‐assembly behavior

Abstract

An organic–inorganic copolymer with polyhedral oligomeric silsesquioxane (POSS) and xanthate moieties in the main chain was synthesized via the polycondensation between 3,13‐di(2‐bromopropionate)propyl double‐decker silsesquioxane (DDSQ) and 1,4‐di(xanthate potassium)butane. This hybrid copolymer was used as the macromolecular chain transfer agent to obtain the organic–inorganic poly(N‐vinylpyrrolidone) (PVPy) copolymers via a reversible addition fragmentation chain transfer/macromolecular design via the interchange of xanthates (RAFT/MADIX) polymerization approach; the polymerization behavior of N‐vinyl pyrrolidone was investigated by means of gel permeation chromatography. It was found that the polymerization was in a living and controlled manner. Transmission electron microscopy (TEM) showed that the organic–inorganic PVPy copolymers with DDSQ in the main chains were microphase‐separated in bulks. Compared to plain PVPy, the organic–inorganic PVPy copolymers displayed the decreased glass transition temperatures (Tgs); the decreased Tgs are attributable to the effect of the introduced DDSQ cages on the packing of PVPy chains as evidenced by means of Fourier transform infrared spectroscopy (FTIR). In water, the organic–inorganic PVPy copolymers can self‐assemble into the spherical nano‐objects with the size of 20–50 nm in diameter. In the self‐assembled nano‐objects, the aggregates of the hydrophobic DDSQ constituted the cores of the polymeric micelles whereas the PVPy chains between the DDSQ behaved as the coronas of the polymeric micelles. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 2949–2961

Organic–Inorganic Polycyclooctadienes with Double-Decker Silsesquioxanes in the Main Chains: Synthesis, Self-Healing, and Shape Memory Properties Regulated with Quadruple Hydrogen Bonds

“…These difunctional POSS molecules have been successfully utilized to prepare the organic–inorganic hybrids via various polymerization approaches, most of which involve step-growth polymerizations. Recently, Zheng and co-workers , reported the combination of step-growth polymerization with controlled/living radical polymerization to introduce POSS cages into the main chains of polymers made from vinyl monomers, for example, poly­( N -isopropylacrylamide) and poly­( N -vinylpyrrolidone). It was of interest to note that the organic–inorganic copolymers displayed typical amphiphilicity and can self-assemble into the organic–inorganic hybrids nanoobjects in aqueous media.…”

Multi-Alkenylsilsesquioxanes as Comonomers and Active Species Modifiers of Metallocene Catalyst in Copolymerization with Ethylene

“…The peaks assigned to chain unsaturation in copolymers occurred in the olefinic region (5.85-4.55 ppm). In the case of E/POSS copolymers, the 13 C NMR spectrum (Figure 7 b) showed the signals at 14.01 ppm (C1 in the spacer), 18.75 ppm (C2 in the These results are consistent with the lower catalytic activity of the ansa-metallocene system in ethylene copolymerization with POSS-10-3 or POSS-10-4 in comparison to ethylene homopolymerization and especially to copolymerization of ethylene with POSS-6-3 ( Figure 2). …”

“…Di-functional POSS derivatives have attracted considerable attention in recent years. Depending on the types of reactive substituents, they have been successfully incorporated into such macromolecules as polyimide [9][10][11], polysiloxane [12], polyamide [13], polyurethane [14], polysulfone [15], vinylidene-arylene copolymer [16], and polyethylene [17], via the polyethylene [17], via the step-growth polymerization process [9][10][11][13][14][15][16]18], or as pendant groups and cross-linkage sites through the coordination copolymerization [17].…”

Organic–Inorganic Polyimides with POSS Cages in the Main Chains: An Impact of POSS R Groups on Morphologies and Properties

“…The as-obtained Na 4 O 14 Si 8 (C 6 H 5 ) 8 was functionalized with the silylation reaction with dichlorosilane bearing a functional group, forming a class of so-called double-decker silsesquioxane (DDSQ) macromers. In the past few years, many difunctional DDSQ macromers carrying a variety of functional groups have been reported. − More recently, Lee and Maleczka et al reported the synthesis of DDSQ macromers with an asymmetrically difunctionalized DDSQ macromer via selective protection with a boronic acid and then an isolation approach. To the best of our knowledge, nonetheless, the R groups ( viz.…”