Synthesis of functional poly(styrene)‐block‐(methyl methacrylate/methacrylic acid) by homogeneous reverse atom transfer radical polymerization: Spherical nanoparticles, thermal behavior, self‐aggregation, and morphological properties

Abstract

This study investigates the use of homogeneous reverse atom transfer radical polymerization for the synthesis of polystyrene (PS) initiated by conventional radical peroxide with copper bromide in the lower oxidation state and a 2,2′‐bypyridine complex as the catalyst. In a second stage, an amphiphilic block copolymer containing methyl methacrylate (MMA) was synthesized via normal atom transfer radical polymerization in two steps, followed by partial hydrolysis of the methyl ester linkage of the MMA block under acidic conditions. The block copolymer PS699‐b‐P(MMA232/MAA58) obtained had a narrow molecular weight dispersity (Ð < 1.3). The structure of the precursor, PS‐b‐PMMA, and resultant polymer, was characterized and verified by FTIR and 1H‐NMR spectroscopy as well as size exclusion chromatography. The self‐aggregation of PS699‐b‐P(MMA232/MAA58) in organic solvents was monitored by UV spectroscopy, whereas the morphology and size of the formed microaggregates were investigated by transmission electron microscopy and dynamic light scattering. The results indicate that this copolymer formed regular spherical reverse micelles with a core–shell structure. The atomic force micrographs of PS699‐b‐P(MMA232/MAA58) showed a rough surface morphology owing to microphase separation of the block copolymer. In addition, thermal characterization was performed by differential scanning calorimetry and thermogravimetric analysis. The glass transition temperature of PS699‐b‐P(MMA232/MAA58) decreased significantly (65°C), when compared to PS and PMMA, suggesting that an enhanced movement of the polymer chains resulted by the segregation of the hydrolyzed P(MMA232/MAA58) block. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

Porous Surface Films With Tunable Morphologies and Hydrophobic Properties Based on Block Copolymer Under the Effects of Thermal Annealing

“…Subsequently PS-b-PAMA were obtained, with a molecular weight approximately between 14,000 and 16,500 Da, see Table 1 and Scheme 1. This was performed in accordance with similar reported procedures (Coca et al, 1998; Hamley, 1998; Beers et al, 1999; Teodorescu et al, 2000; Min et al, 2005; Pizarro et al, 2013, 2015).…”

Effect of annealing and UV-radiation time over micropore architecture of self-assembled block copolymer thin film

“…Infrared spectra were measured on a Bruker Vector 22 FT-IR spectrometer (Bruker Optics GmbH, Inc., Ettlingen, Germany) using OPUS 3.14 software to control the measurements. In previous work [24], this polymeric structure was characterized by 1 H and 13 C NMR analysis studied on a Bruker 400 MHz spectrometer using CDCl 3 the solvent. The structural chemical composition of copolymer films were characterized using Raman spectroscopy with a LabRam 010 instrument from ISA equipped with a 5.5 mW, 632.8 nm He-Ne laser without a filter.…”

“…The PS-b-MMA/MAA was synthesized by ATRP using MMA/PS-Br /CuBr/BPy, in a molar ratio of 100/1/1/2, previously published by our research group [24]. The molecular weight and polydispersity were 10.2·10 4 g/mol and 1.30, respectively.…”

“…[21][22][23]. This work focuses on the microporous structured films formation prepared by solvent casting with annealing above the glass temperature and UV irradiation using the self-assembled amphiphilic PS-b-MMA/MAA block copolymer synthesized by ATRP [24]. With the analysis realized in this work it was possible to investigate the role of physical and chemical interactions between PMAA segments, increasing film surface hydrophilicity, due to hydrogen bonding generated between these chains.…”

Preparation, morphology and sonication time dependence of silver nanoparticles in amphiphilic block copolymers of PEO with polystyrene or PMMA

“…They form films in which the particles are homogeneously dispersed [17,18]. More recently, syntheses of materials with more complex architectures such as amphiphilic double-cylinder-type brushes and their composites with AgNPs [19] using poly(methacrylic acid-co-methyl methacrylate) have been reported. Star copolymers with multi arm blocks can form single molecules with hydrophilic cores in which NPs can be formed [2].…”