Living polymerization of styrene initiated by mercaptan/ε‐caprolactam

The bulk polymerization of styrene initiated by ?‐caprolactam (CL) and n‐dodecyl mercaptan (RSH) has been explored. This novel polymerization system shows living characteristics. For example, the molecular weight of the resulting polymers increases with conversion, and the system has the ability to form diblock copolymers and so forth. The polymer chain end contains thiol and lactam structures, which we have investigated with Fourier transform infrared, ¹H NMR, and ¹³C NMR techniques. Electron spin resonance spectra and theoretical calculations by the Hartree–Fock methods have been used to examine the mechanism. The results reveal that the initial polymerization starts from thiol via a chain‐transfer reaction, and the propagation proceeds by the insertion of a monomer between the terminal group and the intermediate structure of lactam. Finally, the polymerization kinetics have been examined. The polymerization rate varies linearly with the concentration of CL and RSH, and this confirms the mechanism. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4976–4993, 2004     

Synthesis and structural characterization of novel,fluorinated poly(phthalazinone ether)s containing perfluorophenylene moieties

The synthesis and structural characterization of a series of novel, fluorinated poly(phthalazinone ether)s containing perfluorophenylene moieties are described. The monomers, 4‐(4′‐hydroxyaryl)phthalazin‐1(2H)‐ones ( 2a – 2d ), were conveniently and efficiently synthesized from phenols and phthalic anhydride in two steps via 2‐(4′‐hydroxybenzoyl)benzoic acids, which were first obtained by the Friedel–Crafts reaction in good yields and with high stereoselectivity and were then converted into 2a – 2d by fusion with hydrazine. All the polymers were prepared by nucleophilic aromatic substitution (S_NAr) polycondensation between the compounds perfluorobiphenyl and 4‐(4′‐hydroxyaryl)phthalazin‐1(2H)‐ones ( 2a ‐ 2d ). The resulting fluorinated polymers were readily soluble in common organic solvents (e.g., CHCl₃, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, N‐methylpyrrolidone, etc.) at room temperature. Their weight‐average molecular weights and the polydispersities ranged from (7.96–18.25) × 10³ to 1.31–2.71, respectively. Their glass‐transition temperatures varied from 213 to 263 °C. They were all stable up to 390 °C both in air and in argon. The 5% weight‐loss temperatures of these polymers in air and argon ranged from 393–487 to 437–509 °C, respectively. Wide‐angle X‐ray diffraction studies indicated they were all amorphous and could be attributed to the presence of kink nonplanar moiety, phenyl phthalazinone along the polymer backbone. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 925–932, 2004     

Synthesis and characterization of new segmented polyurethanes with side‐chain,liquid‐crystalline chain extenders

Liquid‐crystalline, segmented polyurethanes with methoxy–biphenyl mesogens pendant on the chain extender were synthesized by the conventional prepolymer technique and esterification reaction. Two, side‐chain, liquid‐crystalline (SCLC) polyurethanes with mesogens having spacers of six and eight methylene units were prepared. The structures of the mesogenic units and SCLC polyurethanes were confirmed by Fourier transform infrared spectroscopy and ¹H NMR. Polymer properties were also examined by solubility tests, water uptakes, and inherent viscosity measurements. Differential scanning calorimetry studies indicated that the transition temperature of the isotropic to the liquid‐crystalline phase decreased with increasing spacer length. Wide‐angle X‐ray diffraction (WAXD) studies revealed the existence of liquid‐crystalline phases for both SCLC polyurethanes. Polarized optical microscopic investigations further confirmed the thermotropic liquid‐crystalline behaviors and nematic mesophases of both samples. Thermogravimetric analysis displayed better thermal stabilities for both SCLC polymers and indicated that the presence of mesogenic side chains may increase the thermal stability of segmented polyurethanes. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 290–302, 2004     

Performance of various activators in ethylene polymerization based on an iron(II) catalyst system

Ethylisobutylaluminoxane (EBAO) and its analogues were synthesized by a reaction between an triethylaluminum (Et₃Al)/triisobutylaluminum (i‐Bu₃Al) mixture and 4‐fluorobenzeneboronic acid, phenylboronic acid, or n‐butaneboronic acid and subsequent hydrolysis with water. They were used as cocatalysts in ethylene polymerization catalyzed by an iron complex {[(ArN?C(Me))₂C₅H₃N]FeCl₂, where Ar is 2,6‐diisopropylphenyl}. Polyethylene with a high molecular weight and a narrow molecular weight distribution was prepared with modified EBAOs, and the performance of the iron complex at high polymerization temperatures was greatly improved. The activators for the iron complex also affected the polymerization activity and the molecular weight of the resultant polyethylene. It was suggested that the stereo and electronic effects of the substitute groups of aluminoxane contributed to the improved performance of the new activators. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1093–1099, 2004     

Soluble,saturated‐red‐light‐emitting poly(p‐phenylenevinylene) containing triphenylamine units and cyano groups

A conjugated poly(p‐CN‐phenylenevinylene) (PCNPV) containing both electron‐donating triphenylamine units and electron‐withdrawing cyano groups was prepared via Knoevenagel condensation in a good yield. Gel permeation chromatography suggested that the soluble polymer had a very high weight‐average molecular weight of 309,000. A bright and saturated red emission was observed under UV excitation in solution and film. Cyclic voltammetry showed that the polymer presented quasi‐reversible oxidation with a relatively low potential because of the triphenylamine unit. A single‐layer indium tin oxide/PCNPV/Mg–Ag device emitted a bright red light (633 nm). © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3947–3953, 2004     

Completely biodegradable composites of poly(propylene carbonate) and short,lignocellulose fiber Hildegardia populifolia

The composites of biodegradable poly(propylene carbonate) (PPC) reinforced with short Hildegardia populifolia natural fiber were prepared by melt mixing followed by compression molding. The mechanical properties, thermal properties, and morphologies of the composites were studied via static and dynamic mechanical measurements, thermogravimetric analysis, and scanning electron microscopy (SEM) techniques, respectively. Static tensile tests showed that the stiffness and tensile strength of the composites increased with an increasing fiber content. However, the elongation at break and the energy to break decreased dramatically with the addition of short fiber. The relationship between the experimental results and the compatibility or interaction between the PPC matrix and fiber was correlated. SEM observations indicated good interfacial contact between the short fiber and PPC matrix. Thermogravimetric analysis revealed that the introduction of short Hildegardia populifolia fiber led to a slightly improved thermooxidative stability of PPC. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 666–675, 2004     

Ionic conductivity of multiarm star polymer/LiClO4 electrolytes

A series of polymer electrolytes based on multiarm polymers and lithium salt complexes were characterized by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and impedance measurement. The relationships of conductivity with salt concentration, temperature, and arm numbers are discussed. It is suggested that the star polymer has a higher solvency and ion transfer ability on lithium salts than on linear polymers. The conductivity maximum appeared at a higher salt concentration ([EO]/[Li] = 4). Impedance measurement suggested that the optimum conductivity was 2 × 10^?4 s · cm^?1. The conductivity increased with temperature and the dependence of ionic conductivity on temperature fits the Arrhenius equation. Among the studied systems, the star polymer with a five arm number performs better than other structures. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4195–4198, 2004     

Behavior and surface energies of polybenzoxazines formed by polymerization with argon,oxygen, and hydrogen plasmas

Polybenzoxazine (PBZZ) thin films can be fabricated by the plasma‐polymerization technique with, as the energy source, plasmas of argon, oxygen, or hydrogen atoms and ions. When benzoxazine (BZZ) films are polymerized through the use of high‐energy argon atoms, electronegative oxygen atoms, or excited hydrogen atoms, the PBZZ films that form possess different properties and morphologies in their surfaces. High‐energy argon atoms provide a thermodynamic factor to initiate the ring‐opening polymerization of BZZ and result in the polymer surface having a grid‐like structure. The ring‐opening polymerization of the BZZ film that is initiated by cationic species such as oxygen atoms in plasma, is propagated around nodule structures to form the PBZZ. The excited hydrogen atom plasma initiates both polymerization and decomposition reactions simultaneously in the BZZ film and results in the formation of a porous structure on the PBZZ surface. We evaluated the surface energies of the PBZZ films polymerized by the action of these three plasmas by measuring the contact angles of diiodomethane and water droplets. The surface roughness of the films range from 0.5 to 26 nm, depending on the type of carrier gas and the plasma‐polymerization time. By estimating changes in thickness, we found that the PBZZ film synthesized by the oxygen plasma‐polymerization process undergoes the slowest rate of etching in CF₄ plasma. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4063–4074, 2004     

Influence of solvents on the formation of ultrathin uniform poly(vinyl pyrrolidone) nanofibers with electrospinning

Although there have been many reports on the preparation and applications of various polymer nanofibers with the electrospinning technique, the understanding of synthetic parameters in electrospinning remains limited. In this article, we investigate experimentally the influence of solvents on the morphology of the poly(vinyl pyrrolidone) (PVP) micro/nanofibers prepared by electrospinning PVP solution in different solvents, including ethanol, dichloromethane (MC) and N,N‐dimethylformamide (DMF). Using 4 wt % PVP solutions, the PVP fibers prepared from MC and DMF solvents had a shape like a bead‐on‐a‐string. In contrast, smooth PVP nanofibers were obtained with ethanol as a solvent although the size distribution of the fibers was somewhat broadened. In an effort to prepare PVP nanofibers with small diameters and narrow size distributions, we developed a strategy of using mixed solvents. The experimental results showed that when the ratio of DMF to ethanol was 50:50 (w/w), regular cylindrical PVP nanofibers with a diameter of 20 nm were successfully prepared. The formation of these thinnest nanofibers could be attributed to the combined effects of ethanol and DMF solvents that optimize the solution viscosity and charge density of the polymer jet. In addition, an interesting helical‐shaped fiber was obtained from 20 wt % PVP solution in a 50:50 (w/w) mixed ethanol/DMF solvent. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3721–3726, 2004     

Electrochemical determination of serotonin and the competitive adsorption with dopamine at 5,5-ditetradecyl-2-(2-trimethylammonioethyl)-1,3-dioxane bromide lipid film modified by glassy carbon electrode.

A novel and effective approach to sensitively determine serotonin, known as 5-hydroxytryptamine (5-HT), has been proposed based on a 5,5-ditetradecyl-2-(2-trimethylammonioethyl)-1,3-dioxane bromide (DTDB) self-assembled lipid bilayer membrane modified glassy carbon electrode (DTDB/GCE). A DTDB/GCE shows the strong electrocatalysis for the oxidation of 5-HT, with the peak potential shifted to less positive value of 0.376 V vs. SCE, and effectively eliminates the interference from ascorbic acid (AA), even in the presence of 100-fold concentration of AA. Differential pulse voltammetry (DPV) gave a linear current for 5-HT from 2.0 x 10(-7) to 1.0 x 10(-5) M. At the DTDB/GCE, the oxidation of 5-HT was controlled by the adsorption process; for 5-HT coexisting with DA, the competitive adsorption was observed.