Synthesis and characterization of novel aromatic condensation polymers containing rigid benzoxazole pendent groups

A new aromatic diamine monomer containing benzoxazole substituents was prepared by a multistep synthesis starting from 1,4‐dibromo‐2,5‐difluorobenzene. The diamine was polymerized with commercial aromatic dianhydride or dicarboxylic acid chloride monomers to provide several different poly(amic acid)s and polyamides with their inherent viscosities in the range of 0.24–0.46 dL/g. Thermal properties of these polymers including thermal imidization of poly(amic acid)s into polyimides were investigated by using FTIR, DSC, and TGA. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 178–185, 2004     

Effect of solution properties on nanofibrous structure of electrospun poly(lactic‐co‐glycolic acid)

Electrospinning of poly(lactic‐co‐glycolic acid) (PLGA) in chloroform or 1,1,1,3,3,3‐hexafluoro‐2‐propanol (HFIP) was investigated, focusing on its solution parameters, to develop nonwoven biodegradable nanofibrous structures for tissue engineering. PLGA nanofibers were obtained by electrospinning of 15 wt % PLGA solution and the resulting average fiber diameters were varied with the range of 270–760 nm, depending on solution property. When small amounts of benzyl triethylammonium chloride (BTEAC) was added to the PLGA/chloroform solution, the average diameter was decreased from 760 to 450 nm and the fibers were densely amounted in a straight shape. In addition, the average fiber diameter (270 nm) of nanofibers electrospun from polar HFIP solvent was much smaller than that (760 nm) of nanofibers electrospun from nonpolar chloroform solvent. Therefore, it could be concluded that conductivity or dielectric constant of the PLGA solution was a major parameter affecting the morphology and diameter of the electrospun PLGA fibers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1214–1221, 2006     

Poly(butylene terephthalate)/organoclay nanocomposites prepared by in situ interlayer polymerization and its fiber (II)

Intercalated nanocomposites with poly(butylene terephthalate) (PBT) incorporated between the montmorillonite layers were synthesized from dimethyl terephthalate and 1,4-butane diol by using an in situ interlayer polymerization. The PBT nanocomposites were melt-spun at different organoclay contents to produce monofilaments. The samples were characterized by using wide angle X-ray diffraction, electron microscopy, thermal analysis, and tensile testing. The extent of the clay layer in the PBT was confirmed by using X-ray diffraction and electron microscopy, and the clay layer was found to be highly dispersed on a nanometer scale. The addition of only a small amount of organoclay was enough to improve the thermo-mechanical properties of the PBT hybrid fibers. The hybrids were extruded with various draw ratios (DRs) to examine the tensile mechanical property of the fibers. At DR=1, the ultimate tensile strength of the hybrid fibers increased with the addition of clay up to a critical content and then decreased. However, the initial modulus monotonically increased with increasing amount of organoclay in the PBT matrix. When the DR was increased from 1 to 6, for example, the strength and the initial modulus values of the hybrids containing 3 wt% organoclay decreased linearly.     

An adaptive genetic algorithm for the time dependent inventory routing problem

In this paper we propose an adaptive genetic algorithm that produces good quality solutions to the time dependent inventory routing problem (TDIRP) in which inventory control and time dependent vehicle routing decisions for a set of retailers are made simultaneously over a specific planning horizon. This work is motivated by the effect of dynamic traffic conditions in an urban context and the resulting inventory and transportation costs. We provide a mixed integer programming formulation for TDIRP. Since finding the optimal solutions for TDIRP is a NP-hard problem, an adaptive genetic algorithm is applied. We develop new genetic representation and design suitable crossover and mutation operators for the improvement phase. We use adaptive genetic operator proposed by Yun and Gen (Fuzzy Optim Decis Mak 2(2):161–175, 2003) for the automatic setting of the genetic parameter values. The comparison of results shows the significance of the designed AGA and demonstrates the capability of reaching solutions within 0.5 % of the optimum on sets of test problems.     

Thermal behavior and the determination of the polymer-polymer interaction parameter of polycarbonate and a thermotropic liquid crystalline polymer blends

Summary The surface modification of low-density polyethylene(PE) by liquid phase photograft polymerization with acrylic acid(AA), acrylamide(AM) and glycidyl methacrylate(GMA) was described. The grafting of AA and AM was proved and characterized by electron spectroscopy for chemical analysis(ESCA). It was found that fully hydrophilic surface can be obtained in very short irradiation time. With ESCA and attenuated total reflection infrared spectroscopy(ATR-IR), it can be confirmed that bifunctional monomer GMA was grafted onto the PE film surface. Through further reaction with GMA grafted film, heparin and protamine were immobilized onto the grafted film surface.     

Preparation of ketoprofen‐loaded high‐molecular‐weight poly(vinyl alcohol) gels

High‐molecular‐weight atactic poly(vinyl alcohol) (a‐PVA) gels loaded with (R,S)‐2‐(3‐benzoylphenyl)propionic acid (ketoprofen) were prepared from 5, 6, 7, and 8 g/dL solutions of a‐PVA with a number‐average degree of polymerization of 4000 in an ethylene glycol/water mixture with an aging method to identify the effect of the initial polymer concentration on the swelling behavior, morphology, and thermal properties of a‐PVA gels. Then, the release behavior of ketoprofen from a‐PVA gels was investigated. As the polymer concentration decreased, the ability for network formation decreased, and the degree of swelling of the a‐PVA gels increased. In addition, the enthalpy increased with an increase in the a‐PVA concentration, but the melting temperatures of the gels prepared at different initial polymer concentrations were the same; this indicated that tighter gel networks would be formed by a higher polymer chain density. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation and properties of polyelectrolyte complex sponges composed of hyaluronic acid and chitosan and their biological behaviors

Polyelectrolyte complexes (PECs) composed of chitosan and hyaluronic acid (HA) were prepared in various pH regions and at different weight ratios. At low pHs, there was a strong ionic interaction between NH groups in chitosan and both COO^? and COOH groups in HA due to the deprotonation of HA, whereas weak linkages were formed at high pHs because only the carboxyl groups of HA could interact with NH groups in chitosan. The formation of PECs resulted in a decrease in the crystallinity and thermal stability caused by the interactions between polyions. With variations in the degree of ionization of polyions at various pH conditions, novel PEC sponges were prepared by the freeze drying of PEC solutions. Furthermore, for the evaluation of the wound‐healing effect of PEC sponges with or without an antimicrobial agent (silver sulfadiazine), they were applied to a full‐skin defect of a Wistar rat in vivo. The histology and computerized morphometric analysis of the epidermal healing confirmed the proliferation of fibroblasts in the wound bed and a distinct reduction in infectious agents. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 925–932, 2003     

Eddy characteristics on mass transfer close to free interface

The velocity fluctuations in the immediate vicinity of a free interface were measured with a hot film anemometer. And mass transfer rates and eddy exposure times were analyzed by using the method of deterministic approach. These mass transfer rates were compared with the mass transfer rates by means of concentration measurements in the air-water system. The eddy exposure time distributions obtained from velocity data were skewed toward the lower time value. The contribution of eddies wi:h small exposure time was increased as the liquid became more turbulent. The mass transfer rates were mainly contributed by the Prandtl size eddies and even larger eddies. The mass transfer predictions by the single eddy model employing a deterministic method were in good agreement with the experimental results by independent measurements of concentration.     

Selective Complexation and Membrane Transport of Guanidinium Salts by Calix[6]arene Amides

The p-tert-butylcalix[6]arene hexamide 2 and syn-1,3,5–trimethoxy-2,4,6-triamide 4 were synthesized by reaction of α-chloro-N,N-diethylacetamide and the corresponding calix[6]arenes 1 and 3 , respectively. ¹H NMR spectroscopy shows that 2 is a mixture of different conformations whereas 4 is fixed in a cone conformation. Extraction experiments, (S-L) and (H₂O–CDCl₃) with picrate salts, indicate that 2 complexes both alkali metal (1:2 complex) and guanidinium salts (1:1 complex) but 4 complexes only guanidinium (1:1 complex). Incorporated in supported liquid membranes (Accurel^® / o-nitrophenyl n-octyl ether) the calixarenes 2 and 4 transport guanidinium salts. The hexamide 2 is a more efficient carrier of guanidinium but the syn-1,3,5-trimethoxy-2,4,6-triamide 4 is much more selective. Both 2 and 4 are sufficiently lipophilic to give membranes that are stable over longer periods (weeks).     

Effects of poly(acrylic acid) and poly(ethylene oxide) adsorption on the stability of alumina suspension

The effect of adsorbed polymer on the stability of alumina suspension was investigated. Poly(ethylene oxide) (PEO), poly(acrylic acid) (PAA) and similar kinds of polymer salts were used as a dispersant. The amount of polymer adsorbed on alumina surface and the suspension stability was measured. The pH, molecular weight, and concentration were considered as experimental parameters. PEO shows low affinity on the alumina surface while PAA has high affinity. In the case of PAA adsorption, the surface charge change by polymer adsorption influences suspension stability strongly, but not in the case of PEO adsorption. In simultaneous adsorption of PEO and PAA, the PAA concentration was fixed and PEO concentration was varied. The stability of suspension increased with increasing PEO concentration, and this is partly due to the steric stabilization by adsorption of PAA-PEO complex or adsorption of PEO through pre-adsorbed PAA and the depletion effect of non-adsorbed polymer. Suspension adsorbing sodium salts of PAA and poly(methacrylic acid) (PMA) each showed similar stability. But, when the PEO and these kinds of salts were added together to the suspension, the one with PAA sodium salt could keep a higher stability even with lower molecular weights of PEO compared with suspension with PMA sodium salt.