Synthesis and surface characterization of poly(methyl methacrylate)‐block‐polydimethylsiloxane copolymers from macroazoinitiator

Poly(methyl methyacrylate)‐block‐polydimethylsiloxane (PMMA‐b‐PDMS) copolymers with various compositions were synthesized with PDMS‐containing macroazoinitiator (MAI), which was first prepared by a facile one‐step method in our lab. Results from the characterizations of X‐ray photoelectron spectroscopy (XPS), contact angle measurements, and atomic force microscopy (AFM) showed that the copolymer films took on a gradient of composition and more PDMS segments enriched at the film surfaces, which then resulted in the low surface free energy and little microphase separation at the film surfaces. By contrast, transmission electron microscopy (TEM) analysis demonstrated that distinct microphase separation occurred in bulk. Slight crosslinking of the block copolymers led to much steady morphology and more distinct microphase separation, in particularly for copolymers with low content of PDMS. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesis and surface properties of polydimethylsiloxane‐based block copolymers: poly[dimethylsiloxane‐block‐ (ethyl methacrylate)] and poly[dimethylsiloxane‐block‐(hydroxyethyl methacrylate)]

A polydimethylsiloxane (PDMS) macroazoinitiator was synthesized from bis(hydroxyalkyl)‐terminated PDMS and 4,4′‐azobis‐4‐cyanopentanoic acid by a condensation reaction. The bifunctional macroinitiator was used for the block copolymerization of ethyl methacrylate (EMA) and 2‐(trimethylsilyloxy)ethyl methacrylate (TMSHEMA) monomers. The poly(DMS‐block‐EMA) and poly(DMS‐block‐TMSHEMA) copolymers thus obtained were characterized using Fourier transform infrared and ¹H NMR spectroscopy and differential scanning calorimetry. After the deprotection of trimethylsilyl groups, poly(DMS‐block‐HEMA) and poly(DMS‐block‐EMA) copolymer film surfaces were analysed using scanning electron microscopy and X‐ray photoelectron spectroscopy. The effects of the PDMS concentration in the copolymers on both air and glass sides of films were examined. The PDMS segments oriented and moved to the glass side in poly(DMS‐block‐EMA) copolymer film while orientation to the air side became evident with increasing DMS content in poly(DMS‐block‐HEMA) copolymer film. The block copolymerization technique described here is a versatile and economic method and is also applicable to a wide range of monomers. The copolymers obtained have phase‐separated morphologies and the effects of DMS segments on copolymer film surfaces are different at the glass and air sides. Copyright © 2010 Society of Chemical Industry     

4,4'-偶氮二(4-氰基戊酸)聚乙二醇酯大分子自由基引发剂的合成及表征

采用4,4′-偶氮二(4-氰基戊酸)与五氯化磷反应制备了4,4′-偶氮二(4-氰基戊酰氯)。通过聚乙二醇(PEG-1000)和4,4′-偶氮二(4-氰基戊酰氯)进行缩合反应得到了水溶性的4,4′-偶氮二(4-氰基戊酸)聚乙二醇酯大分子自由基引发剂。利用红外光谱(FT-IR)、紫外光谱(UV)、核磁共振(1H-NMR)、凝胶渗透色谱(GPC)对其结构进行了确认和表征。利用差示扫描量热法(DSC)研究了其热分解性能。结果表明,该引发剂的热分解活化能Ea为120.2 kJ/mol,频率因子Ad为1.165×1014s-1。     

A review on the mechanical and electrical properties of graphite and modified graphite reinforced polymer composites

Carbon materials particularly in the form of sparkling diamonds have held mankind spellbound for centuries, and in its other forms, like coal and coke continue to serve mankind as a fuel material, like carbon black, carbon fibers, carbon nanofibers and carbon nanotubes meet requirements of reinforcing filler in several applications. All these various forms of carbon are possible because of the element's unique hybridization ability. Graphene (a single two-dimensional layer of carbon atoms bonded together in the hexagonal graphite lattice), the basic building block of graphite, is at the epicenter of present-day materials research because of its high values of Young's modulus, fracture strength, thermal conductivity, specific surface area and fascinating transport phenomena leading to its use in multifarious applications like energy storage materials, liquid crystal devices, mechanical resonators and polymer composites. In this review, we focus on graphite and describe its various modifications for use as modified fillers in polymer matrices for creating polymer-carbon nanocomposites.     

Synthesis of macroazoinitiator by direct polycondensation for block copolymerization of styrene and butadiene

Macroazoinitiator (MAI) was prepared from hydroxy‐terminated polybutadiene (HTPB) and 4,4′‐azobis‐4‐cyanopentanoic acid (ACPA) by direct polycondensation in the presence of 1‐methyl‐2‐chloropyridinium iodide (MCPI) at room temperature. This MAI proved to be an effective initiator for thermal polymerization of styrene at 60°C. The resulting products were characterized by viscosity measurements and both IR and NMR spectral studies. The ratio of styrene and butadiene units was calculated from NMR spectral data and scanning electron micrography. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2922–2933, 2001     

Characteristics of polystyrene/organoclay nanocomposites prepared by in‐situ polymerization with macroazoinitiator containing poly(dimethylsiloxane) segment

Polystyrene (PS)/organoclay nanocomposites were prepared by the in situ polymerization of styrene in the presence of organoclay with macroazoinitiator (MAI), composed of repeated sequences of poly(dimethylsiloxane) (PDMS) and azo groups. The X‐ray diffraction patterns and the morphology observed with a transmission electron microscope showed that the dispersion of organoclay in polymer matrix improved as the content of the PDMS segment in the nanocomposite increased. However, negative effects on the rise of glass transition temperatures and the thermal resistance of nanocomposite, measured by differential scanning calorimetry and thermogravimetry, at a high content of the PDMS segment, suggested that organoclay lay preferentially in the PDMS domain. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 2841–2847, 2006     

Synthesis of polydimethylsiloxane‐block‐polystyrene‐block‐polydimethylsiloxane via polysiloxane‐based macroinitiator in supercritical CO2

Polydimethylsiloxane‐block‐polystyrene‐block‐polydimethylsiloxane (PDMS‐b‐PS‐b‐PDMS) was synthesized by the radical polymerization of styrene using a polydimethylsiloxane‐based macroazoinitiator (PDMS MAI) in supercritical CO₂. PDMS MAI was synthesized by reacting hydroxy‐terminated PDMS and 4,4′‐azobis(4‐cyanopentanoyl chloride) (ACPC) having a thermodegradable azo‐linkage at room temperature. The polymerization of styrene initiated by PDMS MAI was investigated in a batch system using supercritical CO₂ as the reaction medium. PDMS MAI was found to behave as a polyazoinitiator for radical block copolymerization of styrene, but not as a surfactant. The response surface methodology was used to design the experiments. The parameters used were pressure, temperature, PDMS MAI concentration and reaction time. These parameters were investigated at three levels (?1, 0 and 1). The dependent variable was taken as the polymerization yield of styrene. PDMS MAI and PDMS‐b‐PS‐b‐PDMS copolymers obtained were characterized by proton nuclear magnetic resonance and infrared spectroscopy. The number‐ and weight‐average molecular weights of block copolymers were determined by gel permeation chromatography. Copyright © 2004 Society of Chemical Industry