Nanostructured Organic−Inorganic Copolymer Networks Based on Polymethacrylate-Functionalized Octaphenylsilsesquioxane and Methyl Methacrylate: Synthesis and Characterization

Abstract

Novel polymethacrylate-functionalized octaphenylsilsesquioxanes (OPS) macromonomer was designed and synthesized, which was employed as nanofiller and cross-linker to copolymerize with MMA to produce OPS/PMMA hybrid nanocomposites with OPS contents ranging from 0 to 1.18 mol %. The synthesis route was that, OPS was brominated to yield polybromo-OPS, and polybromo-OPS was then reacted with BuLi and CO 2 to obtain polycarboxyl-OPS. After that, the carboxyls were converted to chlorocarbonyl groups, and the esterification reaction of polychlorocarbonyl-OPS with 2-hydroxyethyl methacrylate led to polymethacrylate-OPS. Their chemical structures were characterized by means of FTIR, 1 H NMR and 13 C NMR spectra. Moreover, after cleavage of C-Si bond by KF/H 2 O 2 , the position and number of functional groups on the benzene rings of OPS macromonomers and the molecular weight of PMMA in the nanocomposite were investigated in detail by LC-MS and GPC methods, respectively. The prepared OPS macromonomer can result into PMMA significantly improved thermal-chemical stability and apparently increased glass transition temperature. For example, the nanocomposites are insoluble in any common organic solvents due to the formation of three-dimensional networks. Compared to the pure PMMA, the OPS/PMMA nanocomposite with OPS content of only 0.94 mol % exhibits increased 5%-mass-loss temperature and glass transition temperature by 104 and 21 °C, respectively.

Conceptual Design of Large Surface Area Porous Polymeric Hybrid Media Based on Polyhedral Oligomeric Silsesquioxane Precursors: Preparation, Tailoring of Porous Properties, and Internal Surface Functionalization

“…This may be associated to poor reactivity of the tightly tethered vinyl groups to the silicon of the vinylPOSS cages. 40 Possible cage linkage proceeds through a distance only by a few carbon atoms which may be the reason for observing microporosity and large surface areas. 30,39,46 In our phase-separating system, it may additionally be associated to low diffusivity of the precursor (associated with their bulky, rigid molecular structure and high molecular weight).…”

Mechanically Robust Hybrid POSS Thermoplastic Polyurethanes with Enhanced Surface Hydrophobicity

“…Moreover, according to our previous results, not only could POSS enhance thermal stability [ 25 , 26 ], but it could also strengthen the mechanical properties [ 27 ] and retain the optical stability of the materials [ 28 , 29 ] due to its special composition and cage-liked nanostructure. In addition, POSS can be introduced into a polymer matrix by using covalently bonding as a pendent side group [ 30 , 31 , 32 , 33 ] or as end groups [ 34 , 35 ]. For example, Mya KY et al [ 36 ] and Kun Wei et al [ 37 ] reported star-shape POSS grafted PUs, which exhibited enhanced thermal stability and mechanical properties.…”

Thermal and dielectric properties of nanocomposites prepared from reactive graphene oxide and silicon‐containing cycloaliphatic diepoxide

“…Organic/inorganic nanocomposites created by the uniform dispersion of inorganic fillers within a polymeric matrix at the nanometer scale have been proved to be an efficient tool to produce a new material with dramatic improvement in mechanical property, thermal stability, electric property, and gas barrier properties that cannot be achieved by either an inorganic material or organic polymer material alone . Considering that graphene sheet with monoatomic thickness has a large pi‐conjugated structure, the composite obtained by the homogeneous dispersion of graphene in polymer matrix is expected to effectively enhance its dielectric permittivity ( k ), and therefore, it can endow epoxy resin with new function to be potentially used as high‐ k materials in fabricating embedded capacitors, which provide the possibility to embed them into the inner layer of substrate board and thus remove the discrete passive components from the substrate surface .…”