Preparation of narrowly distributed nanoparticles of poly(n‐butyl methacrylate‐co‐vinyl pyrrolidone) through microemulsion polymerization

Narrowly distributed nanoparticles of poly (n‐butyl methacrylate‐co‐vinyl pyrrolidone) were prepared through microemulsion polymerization with a nonionic surfactant of Tween‐80 as emulsifier (6 wt % of the latex) and n‐butanol as coemulsifier. The polymerizations were initiated with benzoylperoxide (BPO), potassium persulfate (KPS), KPS/ferric sulfate (FeSO₄), and BPO/FeSO₄, respectively, where the initiation in the case of BPO/FeSO₄ took place mainly at the interphase between the oil phase and the reaction media. Namely, this interfacial‐initiated microemulsion polymerization resulted in larger particles with relatively narrower particle size distribution as well as higher limiting monomer conversion but lower polymerization rate compared with the polymerization initiated with KPS/FeSO₄. In this article, the influences of initiation method, monomer ratio, and addition of water‐soluble components on microemulsion polymerization and latex particle size were studied to discuss the mechanism of interfacial‐initiated microemulsion polymerization. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2334–2340, 2004     

Pervaporation study of water and tert‐butanol mixtures

The permeation behavior of water/tert‐butanol mixture through Sulzer Pervap2510 hydrophilic poly(vinyl alcohol) membranes was investigated and the effects of feed composition and temperature on separation efficiency of the membranes were studied. The pervaporation experiments were carried out with feed water content varying from 0 to 20 wt % according to the existing industrial needs and with the feed temperature from 60 to 100°C. Over this range, both water flux and separation factor increased with increasing water content and feed temperature. These phenomena may be attributed to (1) the strong interaction between water and the membrane, (2) the decoupling effect of the permeants and the membrane at elevated temperatures, and (3) the steric hindrance effect of branch chain alcohol. The permeability ratio (the ideal separation factor) of water to tert‐butanol across the membrane was calculated and found to follow the same relationship with increasing temperature and water content. Both flux and separation factor obtained from the Pervap2510 membrane in this study were much higher than previous reported values, possible causes for which were analyzed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 4082–4090, 2004     

Preparation and properties of nadic‐end‐capped cyclotriphosphazene‐containing polyimide/carbon fiber composites

New novel fire‐resistant and heat‐resistant cyclotriphosphazene‐containing polyimide resins were prepared in situ by the polymerization of (p‐aminophenoxy)(phenoxy)cyclotriphosphazenes with 3,3′,4,4′‐benzophenonetetracarboxylic acid or 3,3′,4,4′‐diphenylsulfonetetracarboxylic acid and a crosslink agent, 5‐norbornene‐2,3‐dicarboxylic acid and were used as polymer matrix compositing with a woven carbon fiber to prepare nadic‐end‐capped cyclotriphosphazene‐containing polyimide/carbon fiber composites. The thermal stability, flame retardance, morphology of the surface fracture, and some physical properties of the composites were investigated by thermogravimetric analysis, scanning electron microscopy, and a material testing system, respectively. The composites had good thermal stability, flame retardance, and mechanical properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 810–818, 2003     

Nanoscratch testing to assess the fiber adhesion of short‐carbon‐fiber composites

In a composite material, the degree of adhesion between the fiber and the matrix plays an important role in the overall performance of the material. Because the load between the fiber and the matrix is realized throughout the interphase region material, a lot of effort has gone into characterizing the strength of the interphase. In this study, nanoscratch tests on the composite samples were used to provide a relative measure of adhesion in different composite materials. Carbon‐filled nylon 6,6 and polycarbonate resins were evaluated with this method. The carbon fillers we used were polyacrylonitrile‐based carbon fibers sized and surface‐treated for the respective matrix and pitch‐based carbon fibers without any sizing or surface treatment. Tensile and X‐ray photoelectron spectroscopy data for the composites we considered are also presented to compare to the nanoscratch results. It is shown that nanoscratch testing on the composites, with the proposed data analysis, can be an effective tool for determining the relative degree of adhesion between different composites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 328–335, 2007     

Influence of polymerization conditions on the structure and properties of polyethylene/polypropylene in‐reactor alloy synthesized in the gas phase with a spherical Ziegler–Natta catalyst

A spherical TiCl₄/MgCl₂‐based catalyst was used in the synthesis of in‐reactor polyethylene/polypropylene alloys by polyethylene homopolymerization and subsequent homopolymerization of propylene in the gas phase. Different conditions in the ethylene homopolymerization stage, such as monomer pressure and polymerization temperature, were investigated, and their influences on the structure and properties of in‐reactor alloys were studied. Raising the polymerization temperature is the most effective way of speeding up polymerization and regulating the ethylene content of polyethylene (PE)/polypropylene (PP) alloys, but it will cause a greater increase in the PE‐b‐PP block copolymer fraction (named fraction D) than in the fraction of PP‐block‐PE in which the PP segments have low or medium isotacticity (named fraction A). Although changing ethylene monomer pressure could influence the ethylene content of PE/PP alloys slightly, it is an effective way of regulating the structural distribution. Reducing the monomer pressure will evidently increase fractions A and D. The mechanical properties of the alloys, including impact strength and flexural modulus, can be regulated in a broad range with changes in polymerization conditions. These properties are highly dependent on the amount, distribution, and chain structure of fractions A and D. The impact strength is affected by both fraction A and fraction D in a complicated way, whereas the flexural modulus is mainly determined by the amount of fraction A. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2136–2143, 2006     

Characterization and comparison of diblock and triblock amphiphilic copolymers of poly(δ‐valerolactone)

Three types of pegylated amphiphilic copolymers of poly(δ‐valerolactone) (PVL) were copolymerized with methoxy poly(ethylene glycol) (MePEG) and poly(ethylene glycol) (PEG₄₀₀₀ and PEG_10,000), respectively. Pegylation of PVL allowed copolymers possessing amphiphilic property and efficiently self‐assembled to form micelles with a low critical micelle concentration (CMC) in the range of 10^?7–10^?8M. The average molecular weight of copolymers was in the range of 10,000–20,000 Da, and the polydispersity of copolymers was about 1.7–1.8. Higher mobility of low molecular weight PEG (i.e., MePEG and PEG₄₀₀₀) than high molecular weight PEG_10,000 allowed valerolactone ring opening more efficient in terms of PVL/MePEG and PVL/PEG₄₀₀₀ copolymers possessing longer chain length in hydrophobic domain. Pegylated PVL with low CMC and triblock structure was preferred to encapsulate drug during micelle formation. Although all of these amphiphilic copolymers exhibited controlled release character, the micelles formed by triblock copolymer possessed a more stable core‐shell conformation than that by diblock copolymer, and resulted in the release of drug from triblock micelles slower than that from diblock micelles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1836–1841, 2006     

Preparation and ionic conductivity of solid polymer electrolyte based on polyacrylonitrile‐polyethylene oxide

The transparent and flexible solid polymer electrolytes (SPEs) were fabricated from polyacrylonitrile‐polyethylene oxide (PAN‐PEO) copolymer which was synthesized by methacrylate‐headed PEO macromonomer and acrylonitrile. The formation of copolymer is confirmed by Fourier‐transform infrared spectroscopy (FTIR) measurements. The ionic conductivity was measured by alternating current (AC) impedance spectroscopy. Ionic conductivity of PAN‐PEO‐LiClO₄ complexes was investigated with various salt concentration, temperatures and molecular weight of PEO (Mn). And the maximum ionic conductivity at room temperature was measured to be 3.54 × 10^?4 S/cm with an [Li⁺]/[EO] mole ratio of about 0.1. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 461–464, 2006     

Characterization and preparation of new multiwall carbon nanotube/conducting polymer composites by in situ polymerization

Composites based on poly(diphenyl amine) (PDPA) and multiwall carbon nanotubes (MWNTs) were prepared by chemical oxidative polymerization through two different approaches: in situ polymerization and intimate mixing. In in situ polymerization, DPA was polymerized in the presence of dispersed MWNTs in sulfuric acid medium for different molar composition ratios of MWNT and DPA. Intimate mixing of synthesized PDPA with MWNT was also used for the preparation of PDPA/MWNT composites. Transmission electron microscopy revealed that the diameter of the tubular structure for the composite was 10–20 nm higher than the diameter of pure MWNT. Scanning electron microscopy provided evidence for the differences in the morphology between the MWNTs and the composites. Raman and Fourier transform IR (FTIR) spectroscopy, thermogravimetric analysis, X‐ray diffraction, and UV–visible spectroscopy were used to characterize the composites and reveal the differences in the molecular level interactions between the components in the composites. The Raman and FTIR spectral results revealed doping‐type molecular interactions and coordinate covalent‐type interactions between MWNT and PDPA in the composite prepared by in situ polymerization and intimate mixing, respectively. The backbone structure of PDPA in the composite decomposed at a higher temperature (>340°C) than the pristine PDPA (～300°C). This behavior also favored the molecular level interactions between MWNT and PDPA in the composite. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3721–3729, 2006     

Nanosized silica‐supported metallocene/MAO catalyst for propylene polymerization

A nanosized silica particle was used as the support to prepare an Et[Ind]₂ZrCl₂/MAO catalyst for propylene polymerization of polypropylene. The catalyst and the polymer produced were characterized with nitrogen adsorption, ICP, DSC, SEM, TEM, XRD, solution viscometer, ¹³C NMR and optical microscopy. The effects of polymerization temperature and [Al]/[Zr] ratio on catalyst activity and polymer melting point were investigated. Under identical reaction conditions, nanosized catalyst exhibited better polymerization activity than the microsized catalyst (e.g., the former had 64% higher activity than the latter at the optimum polymerization temperature (50°C) and [Al]/[Zr] = 570). DSC results indicated that polymer melting point increased with the increase of [Al]/[Zr] ratio and with the decrease of polymerization temperature. XRD results showed that the percentage of γ crystals increased with decreasing [Al]/[Zr] ratio. Electron microscopic results showed that the polymer particle size increased with increasing polymerization temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2573–2580, 2006     

Synthesis and properties of polystyrene‐b‐poly(ethylene oxide)‐b‐polystyrene triblock copolymers

A series of well‐defined and property‐controlled polystyrene (PS)‐b‐poly(ethylene oxide) (PEO)‐b‐polystyrene (PS) triblock copolymers were synthesized by atom‐transfer radical polymerization, using 2‐bromo‐propionate‐end‐group PEO 2000 as macroinitiatators. The structure of triblock copolymers was confirmed by ¹H‐NMR and GPC. The relationship between some properties and molecular weight of copolymers was studied. It was found that glass‐transition temperature (T_g) of copolymers gradually rose and crystallinity of copolymers regularly dropped when molecular weight of copolymers increased. The copolymers showed to be amphiphilic. Stable emulsions could form in water layer of copolymer–toluene–water system and the emulsifying abilities of copolymers slightly decreased when molecular weight of copolymers increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 727–730, 2006