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     

Novel,organosoluble, light‐colored fluorinated polyimides based on 2,2′‐bis(4‐amino‐2‐trifluoromethylphenoxy)biphenyl or 2,2′‐bis(4‐amino‐2‐trifluoromethylphenoxy)‐1,1′‐binaphthyl

Two series of fluorinated polyimides were prepared from 2,2′‐bis(4‐amino‐2‐trifluoromethylphenoxy)biphenyl ( 2 ) and 2,2′‐bis(4‐amino‐2‐trifluoromethylphenoxy)‐1,1′‐binaphthyl ( 4 ) with various aromatic dianhydrides via a conventional, two‐step procedure that included a ring‐opening polyaddition to give poly(amic acid)s, followed by chemical or thermal cyclodehydration. The inherent viscosities of the polyimides ranged from 0.54 to 0.73 and 0.19 to 0.36 dL/g, respectively. All the fluorinated polyimides were soluble in many polar organic solvents, such as N,N‐dimethylacetamide and N‐methylpyrrolidone, and afforded transparent and light‐colored films via solution‐casting. These polyimides showed glass‐transition temperatures in the ranges of 222–280 and 257–351 °C by DSC, softening temperatures in the range of 264–301 °C by thermomechanical analysis, and a decomposition temperature for 10% weight loss above 520 °C both in nitrogen and air atmospheres. The polyimides had low moisture absorptions of 0.23–0.58%, low dielectric constants of 2.84–3.61 at 10 kHz, and an ultraviolet–visible absorption cutoff wavelength at 351–434 nm. Copolyimides derived from the same dianhydrides with an equimolar mixture of 4,4′‐oxydianiline and diamine 2 or 4 were also prepared and characterized. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2416–2431, 2004     

Novel aromatic polyamides bearing pendent diphenylamino or carbazolyl groups

Two new diamines, 2,4‐diaminotriphenylamine ( 3 ) and N‐(2,4‐diaminophenyl)carbazole ( 4 ), were synthesized via the cesium fluoride‐mediated aromatic substitution reactions of 1‐fluoro‐2,4‐dinitrobenzene with diphenylamine and carbazole, followed by palladium‐catalyzed hydrazine reduction. Amorphous and soluble aramids having pendent diphenylamino and carbazolyl groups were prepared by the phosphorylation polycondensation of aromatic dicarboxylic acids with diamines 3 and 4 , respectively. The aramids derived from diamine 3 had sufficiently high molecular weights to permit the casting of flexible and tough films. They exhibited excellent mechanical properties and moderately high softening temperatures in the 221–298 °C range. However, the reactions of diamine 4 with aromatic diacids gave relatively lower molecular weights products that could not afford flexible films. For a comparative purpose, the parent aramids derived from m‐phenylenediamine and aromatic diacids were also prepared and characterized. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3302–3313, 2004     

Instanton vacuum in thermal QCD

The effects of instanton-anti-instanton interactions in high-temperature QCD with colour SU(2) are studied with and without quarks. The instanton potential proves to have no repulsive core, thus creating troubles with the definition of nonperturbative contributions to physical quantities. Also the chiral condensate is calculated, and it is shown to vanish if number of quark flavoursN _f≧2, whereas forN _f=1 it is nonzero for the arbitrary high temperature.     

Synthesis and characterization of wholly aromatic poly(azomethine)s containing donor–acceptor triphenylamine moieties

N‐(4‐nitrophenyl)‐4′,4″‐bisformyl‐diphenylamine was synthesized from N‐(4‐nitrophenyl)‐diphenylamine by the Vilsmeier‐Haack reaction. Soluble aromatic poly(azomethine)s (PAMs) were prepared by the solution polycondensation of N‐(4‐nitrophenyl)‐4′,4″‐bisformyl‐diphenylamine and aromatic diamine in N‐methyl‐2‐pyrrolidone (NMP) at room temperature under reduced pressure. All the PAMs are highly soluble in various organic solvents, such as N,N‐dimethylacetamide (DMAc), chloroform (CHCl₃), and tetrahydrofuran (THF). Differential scanning calorimetry (DSC) indicated that these PAMs had glass‐transition temperatures (T_gs) in the range of 170–230 °C, and a 10% weight‐loss temperatures in excess of 490 °C with char yield at 800 °C in nitrogen higher than 60%. These PAMs in NMP solution showed UV‐Vis charge‐transfer (CT) absorption at 405–421 nm and photoluminescence peaks around 462–466 nm with fluorescence quantum efficiency (Φ_F) 0.10–0.99%. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of these PAMs can be determined from cyclic voltammograms as 4.86–5.43 and 3.31–3.34 eV, respectively. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4921–4932, 2007     

On a Quadratic Optimization Problem with Equality Constraints

The constrained optimization problem with a quadratic cost functional and two quadratic equality constraints has been studied by Bar-on and Grasse, with positive-definite matrix in the objective. In this note, we shall relax the matrix in the objective to be positive semidefinite. A necessary and sufficient condition to characterize a local optimal solution to be global is established. Also, a perturbation scheme is proposed to solve this generalized problem.     

Three-dimensional steady supersonic duct flow using Lagrangian formulation

In this paper, numerical simulation of three-dimensional supersonic flow in a duct is presented. The flow field in the duct is complex and can find its applications in the inlet of air-breathing engines. A unique streamwise marching Lagrangian method is employed for solving the steady Euler equations. The method was first initiated by Loh and Hui (1990) for 2-D steady supersonic flow computations and then extended to 3-D computation by the present authors Loh and Liou (1992). The new scheme is shown to be capable of accurately resolving complicated shock or contact discontinuities and their interactions. In all the computations, a free stream of Mach numberM=4 is considered.This article was processed using Springer-Verlag T_EX Shock Waves macro package 1.0 and the AMS fonts, developed by the American Mathematical Society.     

Synthesis and properties of noncoplanar rigid‐rod aromatic polyhydrazides and poly(1,3,4‐oxadiazole)s containing phenyl or naphthyl substituents

Two new phenyl‐ and naphthyl‐substituted rigid‐rod aromatic dicarboxylic acid monomers, 2,2′‐diphenylbiphenyl‐4,4′‐dicarboxylic acid ( 4 ) and 2,2′‐di(1‐naphthyl)biphenyl‐4,4′‐dicarboxylic acid ( 5 ), were synthesized by the Suzuki coupling reaction of 2,2′‐diiodobiphenyl‐4,4′‐dicarboxylic acid dimethyl ester with benzeneboronic acid and naphthaleneboronic acid, respectively, followed by alkaline hydrolysis of the ester groups. Four new polyhydrazides were prepared from the dicarboxylic acids 4 and 5 with terephthalic dihydrazide (TPH) and isophthalic dihydrazide (IPH), respectively, via the Yamazaki phosphorylation reaction. These polyhydrazides were amorphous and readily soluble in many organic solvents. Differential scanning calorimetry (DSC) indicated that these hydrazide polymers had glass transition temperatures in the range of 187–234 °C and could be thermally cyclodehydrated into the corresponding oxadiazole polymers in the range of 300–400 °C. The resulting poly(1,3,4‐oxadiazole)s exhibited T_g's in the range of 252–283 °C, 10% weight‐loss temperature in excess of 470 °C, and char yield at 800 °C in nitrogen higher than 54%. These organo‐soluble polyhydrazides and poly(1,3,4‐oxadiazole)s exhibited UV–Vis absorption maximum at 262–296 and 264–342 nm in NMP solution, and their photoluminescence spectra showed maximum bands around 414–445 and 404–453 nm, respectively, with quantum yield up to 38%. The electron‐transporting properties were examined by electrochemical methods. Cyclic voltammograms of the poly(1,3,4‐oxadiazole) films cast onto an indium‐tin oxide (ITO)‐coated glass substrate exhibited reversible reduction redox with E_onset at ?1.37 to ?1.57 V versus Ag/AgCl in dry N,N‐dimethylformamide solution. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6466–6483, 2006