Preparation and characterization of optically active polystyrene via a chiral nitroxide‐mediated polymerization

2,2,6,6‐Tetramethyl‐4‐[d‐(+)‐10‐camphorsulfonyl]‐1‐piperidinyloxy was synthesized and used as a chiral nitroxide for the bulk polymerizations of styrene initiated with benzoyl peroxide (BPO), tetraethylthiuram disulfide (TETD), and thermal initiation. The results showed that the polymerizations proceeded in a controlled/living way; that is, the kinetics presented approximately first‐order plots, and the number‐average molecular weights of the polymers with narrow molecular weight distributions (weight‐average molecular weight/number‐average molecular weight) increased with the monomer conversion linearly. The molecular weight distributions in the case of thermal initiation were narrower than those in the case of BPO and TETD, whereas the polymerization rate with BPO or TETD as an initiator was obviously faster than that with thermal initiation. In addition, successful chain‐extension reactions were carried out, and the structures of the obtained polymers were characterized by gel permeation chromatography and ¹H NMR. The specific rotations of the polymers were also measured by polarimetric analysis. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1522–1528, 2006     

Sulfonated poly(aryl ether ether ketone ketone)s containing fluorinated moieties as proton exchange membrane materials

A series of sulfonated poly(aryl ether ether ketone ketone)s statistical copolymers with high molecular weights were synthesized via an aromatic nucleophilic substitution polymerization. The sulfonation content (SC), defined as the number of sulfonic acid groups contained in an average repeat unit, could be controlled by the feed ratios of monomers. Flexible and strong membranes in sodium sulfonate form could be prepared by the solution casting method, and readily transformed to their proton forms by treating them in 2 N sulfuric acid. The polymers showed high T_gs, which increased with an increase in SC. Membranes prepared from the present sulfonated poly(ether ether ketone ketone) copolymers containing the hexafluoroisopropylidene moiety (SPEEKK‐6F) and copolymers containing the pendant 3,5‐ditrifluoromethylphenyl moiety (SPEEKK‐6FP) had lower water uptakes and lower swelling ratios in comparison with previously prepared copolymers containing 6F units. All of the polymers possessed proton conductivities higher than 1 × 10^?2 S/cm at room temperature, and proton conductivity values of several polymers were comparable to that of Nafion at high relative humidity. Their thermal stability, oxidative stability, and mechanical properties were also evaluated. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2299–2310, 2006     

Crystal structure and morphology of phenyl‐capped tetraaniline in the leucoemeraldine oxidation state

A series of crystals of phenyl‐capped tetraaniline in the leucoemeraldine oxidation state were obtained at different isothermal temperatures and were observed directly under transmission electron microscope. The crystals obtained at higher temperatures exhibit more perfect structures than those obtained at lower temperatures. Both the lamella thickness and the crystal size increase with crystallization temperature. The tetraaniline is apt to form larger scale crystals under lower degree of supercooling. However, their crystal structures keep steady with the crystallization temperature. The tetramer was found to adopt a monoclinic lattice with unit cell parameter of a = 13.93 Å, b = 8.82 Å, c = 23.20 Å, and β = 95.03°, as determined using electron diffraction tilting method combined with wide‐angle X‐ray diffraction experiment. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 764–769, 2006     

Independence of the brittle–ductile transition from the rubber particle size for impact‐modified poly(vinyl chloride)

A series of acrylic impact modifiers (AIMs) with different particle sizes ranging from 55.2 to 927.0 nm were synthesized by seeded emulsion polymerization, and the effect of the particle size on the brittle–ductile transition of impact‐modified poly(vinyl chloride) (PVC) was investigated. For each AIM, a series of PVC/AIM blends with compositions of 6, 8, 10, 12, and 15 phr AIM in 100 phr PVC were prepared, and the Izod impact strengths of these blends were tested at 23 °C. For AIMs with particle sizes of 55.2, 59.8, 125.2, 243.2, and 341.1 nm, the blends fractured in the brittle mode when the concentration of AIM was lower than 10 phr, whereas the blends showed ductile fracture when the AIM concentration reached 10 phr. It was concluded that the brittle–ductile transition of the PVC/AIM blends was independent of the particle size in the range of 55.2–341.1 nm. When the particle size was greater than 341.1 nm, however, the brittle–ductile transition shifted to a higher AIM concentration with an increase in the particle size. Furthermore, the critical interparticle distance was found not to be the criterion of the brittle–ductile transition for the PVC/AIM blends. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 696–702, 2006     

Reinforcement effect of MAA on nano‐CaCo3‐filled EPDM vulcanizates and possible mechanism

Methacrylic acid (MAA) was used as in situ surface modifier to improve the interface interaction between nano‐CaCO₃ particle and ethylene–propylene–diene monomer (EPDM) matrix, and hence the mechanical properties of nano‐CaCO₃‐filled EPDM vulcanizates. The results showed that the incorporation of MAA improved the filler–matrix interaction, which was proved by Fourier transformation infrared spectrometer (FTIR), Kraus equation, crosslink density determination, and scanning electron microscope (SEM). The formation of carboxylate and the participation of MAA in the crosslinking of EPDM indicated the strong filler–matrix interaction from the aspect of chemical reaction. The results of Kraus equation showed that the presence of MAA enhanced the reinforcement extent of nano‐CaCO₃ on EPDM vulcanizates. Crosslink density determination proved the formation of the ionic crosslinks in EPDM vulcanizates with the existence of MAA. The filler particles on tensile fracture were embedded in the matrix and could not be observed obviously, indicating that a strong interfacial interaction between the filler and the matrix had been achieved with the incorporation of MAA. Meanwhile, the presence of MAA remarkably increased the modulus and tensile strength of the vulcanizates, without negative effect on the high elongation at break. Furthermore, the ionic bond was thought to be formed only on filler surface because of the absolute deficiency of MAA, which resulted in the possible structure where filler particles were considered as crosslink points. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1226–1236, 2006     

Slow crack growth in blends of HDPE and model copolymers

The resistance to slow crack growth (SCG) was measured in binary blends of high density polyethylene (HDPE) and 5–10% concentrations of model ethylene-butene random copolymers by measuring the time to failure (t_f) under a constant stress intensity. An increase of t_f with the addition of the copolymer if the copolymer could crystallize and the increase was greater the higher branch density. The copolymer with 117 branches/1000C could not crystallize and therefore its blend had a t_f that was less than that of the HDPE. The fracture energies of the blends as determined by their resistance to SCG were compared with the energy by rapid fracture, J_c, as previously measured by Rhee and Crist. It is concluded that SCG is more sensitive to variations in the microstructure than is rapid fracture and that the differences in SCG behavior can be qualitatively explained in terms of the differences in microstructure of the blends. ©1995 John Wiley & Sons, Inc.     

Asymmetric synthesis XXVII: Asymmetric catalytic trimethylsilylcyanation of aldehydes by novel Ti-chiral Schiff base complexes

Enantioselective catalytic trimethylsilylcyanations of aldehydes with 48% to 92% e.e. have been studied using the novel Ti-chiral Schiff base complexes. We have found that the catalyst led to high enantoselectivity when the molar ratio of the Schiff base 1 to Ti(O-i-Pr)₄ was 2:1.     

Amperometric detection of catecholamines with liquid chromatography at a novelly constructed prussian blue chemically modified electrode

A novel Prussian blue chemically modified electrode (CME) was constructed and characterized for liquid chromatography electrochemical detection (LCEC) of catecholamines. Both anodic and cathodic peaks could be obtained by monitoring at constant applied potential at anodic and slightly cathodic potential ranges (0.3-0.7 and -0.2-0.1 V vs. SCE), respectively. When arranged in a series configuration, using the modified electrodes as generating and collecting detectors, extremely high effective collection efficiencies of 0.91 (for norepinephrine) and 0.58 (for dihydroxyphenylacetic acid) were achieved in dual-electrode LCEC for catecholamines; and a linear response range over 3 orders of magnitude and a detection limit of 10 pg were obtained with a downstream CME as the indicating detector.     

Sequential transition States and the valley-ridge inflection point in the formation of a semibullvalene

[structure: see text] Two sequential transition states are calculated at the B3LYP/6-31G(d,p) level for the deazetization of 3b. The intrinsic reaction coordinate for loss of nitrogen passes through a transition state and then a valley-ridge inflection point and ultimately leads to the transition state for the Cope rearrangement of semibullvalene 4b. The energetic and geometrical consequences are discussed.