Precision Synthesis of a Fluorinated Polyhedral Oligomeric Silsesquioxane-Terminated Polymer and Surface Characterization of Its Blend Film with Poly(methyl methacrylate)

Abstract

Incompletely condensed, fluorinated polyhedral oligomeric silsesquioxane with the highly reactive group of trisodium silanolate was used for the synthesis of an initiator for atom transfer radical polymerization. The initiator was applied to solution polymerization of methyl methacrylate (MMA) in the presence of a copper complex. The polymerization proceeded in a living fashion, providing tadpole-shaped polymers with an “inorganic head” of polyhedral oligomeric silsesquioxane (POSS) and an “organic tail” of well-defined PMMA. A blend film composed of the tadpole-shaped polymer and a matrix PMMA was annealed at 180 °C for 5 days and then analyzed by neutron reflectometry, X-ray photoelectron spectroscopy, and contact angle measurement. These analyses revealed that the tadpole-shaped polymer was preferentially populated at the air/polymer interface, and the outermost layer of the film was almost completely covered by the POSS heads. This was mainly due to the low surface free energy of the fluorinated POSS moiety. Owing to this unique structure, the blend film showed strong resistance against Ar+ ion etching, despite the overall POSS content was only 2 wt %.

Structure-Gas Transport Property Relationships of Poly(dimethylsiloxane-urethane) Nanocomposite Membranes

“…The POSS portion combines the features of organosilicon compounds and possess low free energy (Youngblood and McCarthy, 1999). Thus, the enrichment of the POSS portion at the surface could occur upon incorporating the organicinorganic amphiphile into organic polymer and the surface hydrophobicity of materials will significantly be enhanced (Koh, 2005). Hence, the hydrophobic part of POSS was chosen to study the effect of POSS on surface morphology of polymers and thereby influencing the permeability and selectivity of gases.…”

Tadpole-Shaped POSS-Based Copolymers and the Aggregation Behavior at Air/Water Interface

“…Subsequently, a variety of POSS-based small molecules or polymers were synthesized and the different self-assembly behavior was achieved as well [8][9][10][11][12]. Wamke et al [13] successfully synthesized two open-cage TSiO-POSS and DSiB-POSS with short alkyl chains and compared the interfacial property of Langmuir monolayer.…”

POSS/Polyurethane Hybrids and Nanocomposites: A Review on Preparation, Structure and Performance

“…13 From the standpoint of molecular design, the organic and inorganic phases are combined with covalent bond to form POSS, is a new type of organic-inorganic hybrid material. [14][15][16][17][18][19][20][21][22][23][24] It is reported that POSS exists in the following structures: random, ladder, cage, and partial cage. 25,26 POSS can be incorporated into polyurethanes by physical blending and chemical modifications.…”