Self-Assembly of Methacrylic Nanostructured Copolymers Containing Polyhedral Oligomeric Silsesquioxanes

Abstract

Two hybrid copolymer series obtained by free-radical copolymerization of methacrylcyclohexyl Polyhedral oligomeric silsesquioxane (POSS) with butyl methacrylate or 2-ethylhexylmethacrylate were characterized by 1 H-NMR spectroscopy, gel permeation chromatography (GPC), X-rays Diffraction (XRD), differential scanning calorimetry (DSC) and thermo-gravimetric analysis (TGA). Reactivity ratios were calculated by low yield composition data suggesting the formation of random copolymers with low probability of poly-POSS sequences. XRD studies showed the crystallization behaviour of the inorganic phase independently on the POSS content; however sample processing by solvent casting effectively hindered the copolymer self-assembling ability. DSC suggests the formation of polyphasic structures with T g increasing with POSS content, and with endothermal peaks occurring at higher temperature. Finally TGA shows an improved thermal stability of hybrid copolymers with char yield correlated to the level of inorganic phase.

Anchor Effect in Polymerization Kinetics: Case of Monofunctionalized POSS

“…This means that MMA is preferentially incorporated into the copolymer and the amount of POSS introduced increases as the reaction progresses. The difference in the reactivity of the two comonomers can be explained by the significant difference in their molecular size and in the steric hindrance they exert [32]. Very recently, a higher reactivity of MMA and butyl methacrylate in copolymerization with methacryloxypropyl-heptaisobutyl POSS was also reported [33].…”

Recent Developments in the Chemistry of Cubic Polyhedral Oligosilsesquioxanes

“…597 The XRD pattern of T 8 Cy 7 (CH 2 ) 3 OC-(dO)C(dCH 2 )Me shows sharp reflections at 2θ ) 7.83°, 10.46°, 11.61°, 18.14°, and 18.80°; copolymers of this monomer with n-BuOC(dO)C(CdCH 2 )Me show a reflection at 2θ ) 7.2°indicative of crystallinity in the polymer. 598 WAXS patterns show that incorporation of T 8 Cy 7 (CH 2 ) 3 -OC(O)C(dCH 2 )Me into dimethacrylate networks leads to a loss of crystallinity. 563 The WAXS pattern of T 8 Ph 7 (CH 2 ) 3 OCH 2 CH(O)CH 2 shows intense peaks at 2θ ) 8.4°, 9.1°, and 19°, 264 while that for T 8 Ph 7 (CH 2 ) 3 -OC(O)C(dCH 2 )Me shows sharp peaks that are retained in copolymers with poly(octafluoropentyl acrylate), again indicative of POSS aggregation.…”

Synthesis of Photoresponsive Spiropyran‐Based Hybrid Polymers and Controllable Light‐Triggered Self‐Assembly Study in Toluene

“…One important aspect that worthy to be studied is the self‐assembly behavior of these hybrid polymers with novel architectures. Recent self‐assembly studies of POSS‐containing polymers show that the introduction of POSS units can raise the thermal stability of the aggregates,22 decrease the dielectric constant of the aggregates,23, 24 prepare novel liquid crystal materials25 and tissue engineering devices,26 increase the thermal response,27 and shape recovery capabilities of the materials,28, 29 etc. Moreover, the incorporation of hydrophobic (hydrophilic) POSS into a hydrophilic (hydrophobic) polymer endows the polymer with amphipathy 30–37.…”