Effect of fluoropolymer antidripping agent on the microstructure and properties of polyesters

Poly(ethylene terephthalate) (PET) is of excellent mechanical properties and melt processability and is widely used as raw material for textile fibers. However, the flame retardant properties of PET were rather poor, and both reactive and additive phosphorus- and halogen-containing compounds have been employed to enhance the reaction-to-fire properties while the meltdripping behaviour during burning hasn’t been handled properly with the flame retardants. In this work, fluoropolymer was blended with both pure PET (pPET) and reactive phosphorus-containing flame retarded copolyester (fPET), and the flame retardance and char formation and mechanical properties of the resulted pPET and fPET blends were investigated. The tensile strengths of modified pPET samples were worsen whereas those of modified fPET samples were improved at low concentrations. The initial thermal degradation in nitrogen was accelerated remarkably for the two polyesters with fluoropolymer. The oxygen indices of the all modified samples were reduced while char formation and meltdripping suppression were encouraged. The apparent melt viscosity and elasticity for the two polyesters were gained much with antidripping agent. Therefore, fluoropolymer improved char formation of the two polyesters based on the gaseous phase mechanism while the partial suppression of meltdripping behavior and the decrease of mechanical properties mainly originated from the increase of melt viscosity via fibrillation for pPET.     

CFD Simulation of Liquid Film Flow on Inclined Plates

A two‐phase flow CFD model using the volume of fluid (VOF) method is presented for predicting the hydrodynamics of falling film flow on inclined plates, corresponding to the surface texture of structured packing. Using the proposed CFD model the influence of the solid surface microstructure, liquid properties and gas flow rate on the flow behavior was investigated. From the simulated results it was shown that under the condition of no gas flow the liquid flow patterns are dependent on the microstructure of the plates, and proper microstructuring of the solid surface will improve the formation of a continuous liquid film. It was also found that liquid properties, especially surface tension, play an important role in determining the thin‐film pattern. However, there are very different liquid film patterns under the action of gas flow. Thinner liquid films break easily, but thicker liquid films can remain continuous even at higher gas flow rates, which demonstrates that all factors affecting the liquid film thickness will affect the liquid film patterns under conditions of counter‐current two‐phase flow.     

Synthesis and aqueous solution behaviors of sodium sulfonate‐terminated dendritic poly(ester‐amine)

Sodium sulfonate‐terminated dendritic poly(ester‐amine) (SPEA) was synthesized by sulfonation of acrylic double bond‐terminated dendritic poly(ester‐amine) (APEA) with sodium hydrogen sulfite (NaHSO₃) in mixture of diglycol and 2‐butanone under normal pressure. The structure of SPEA was characterized by IR, ¹H‐NMR, and elemental analysis. SPEA was water‐soluble. 1.0–40.0% (mass) SPEA aqueous solutions appeared as dilatant fluid. When pH value varied from 1.5 to 12.0, the viscosity of 1–5% (mass) SPEA aqueous solutions changed very small, and the electric conductivity almost kept stable within pH 3.0–10.0. The relationship between the viscosity and the concentration of SPEA water solutions was similar to that of NaCl water solutions. The surface tension of SPEA water solutions was lower than that of polyethylene glycol 2000 water solutions with the same concentration. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Novel blood-compatible waterborne polyurethane using chitosan as an extender

A series of novel block polymers of polyurethane (PU) and chitosan have been prepared in two steps. The first step is the preparation of PU prepolymer, obtained from polytetramethylene oxide glycol (PTMO, M_n = 1000), isophrone diisocyanate (IPDI), and 2,2′-dimethylol propionic acid (DMPA), followed by ionizing PU prepolymer with triethylamine (TEA). The second step involves PU chain-extended by water-soluble chitosan of low molecular weight (M_n = 5000) by self-emulsion polymerization method. The sizes of the latex particles, morphology, and copolymer architecture have been characterized by dynamic light scattering (DLS), general tensile test, infrared spectroscopy (IR), surface contact angle measurement, and transmission electron microscopy (TEM). Furthermore, it shows that the addition of chitosan remarkably increases anticoagulative property of PU elastomers confirmed by the recalcification time. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effects of three crosslinkers on colored pH‐responsive core–shell latexes

Environmentally responsive hydrogels have become attractive research subjects for many applications. In this work, a series of pH‐sensitive and color‐changing nanoparticles (nanogels) with core–shell structures were synthesized. The cores were blue latex particles synthesized by a miniemulsion technique with styrene and methacrylic acid as monomers and Neozapon Blue 807 as a dye. The shell was a pH‐sensitive polymer that was precipitation‐polymerized onto the core from 2‐(diethylamino) ethyl methacrylate with N,N′‐methylenebisacrylamide, poly(propylene glycol) diacrylate, and divinylbenzene as crosslinking agents. In the resultant latexes, the color was observed to change from deep blue to pale blue as the pH of the system was changed from a high of 10 to a low of 3. The synthesized latexes and particles (gels) were then characterized with an ultraviolet–visible spectrometer, dynamic light scattering, Fourier transform infrared, and nuclear magnetic resonance. Atomic force microscopy was also used to investigate the different morphologies of the particles after the synthesized latexes were dried at different pH values. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and characterization of metal-complex imprinted PVDF hollow fiber membranes

Using nickel-2,2′-dipyridyl complex as a template, N-vinyl-2-pyrrolidone as the metal coordination functional monomer, and ethylene glycol dimethacrylate as the crosslinker, polyvinylidene fluoride (PVDF) hollow fiber ultrafiltration membrane as the supported membrane, metal complex imprinted polymeric membranes were prepared. The association constant of template-monomer interaction in the prepolymerization solution was estimated to be 4.38 × 10⁴ (L/mol)² by spectrophotometric titration analysis. The attenuated total reflection Fourier transform infrared spectroscopy and scanning electron micrograph characterization indicated that the surface of the support PVDF membrane was completely coated by the imprinted polymer layer after modification. The imprinted membranes exhibited the selective permeability for the template in certain nickel acetate solution. The molecularly imprinted membranes gave higher permeation separation factors at about pH 6, whereas increasing pressure would lower the separation ability. The effects of ion concentration, cations and counterions, ligand selectivity, pH, and trans-membrane pressure were investigated and the permeation performances of the imprinted membranes could be regarded as facilitated transport mechanism. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of post‐treatments on the properties of porous poly(vinyl alcohol) membranes

Porous poly(vinyl alcohol) (PVA) membranes were prepared by a phase‐inversion method. The influence of chemical crosslinking and heat treatments on the swelling degree, resistance to compaction, mechanical strength, and morphology of porous PVA membranes was extensively studied. The crosslinking degree and crystallinity of the membranes, calculated from IR spectra, increased with the treatment time. The porosity, calculated on the basis of swelling experiments, showed a decreasing trend for heat‐treated membranes but remained almost at a constant value for crosslinked membranes. Such a change was further proved with scanning electron microscopy pictures. The behavior was explained by the rearrangement of PVA chains during the heat‐treatment process, which led to morphological changes in the membranes. The mechanical properties of the porous membranes in dry and wet states were measured, and a great difference was observed between crosslinked and heat‐treated membranes in the dry and wet states. The crosslinked membranes showed good mechanical properties in the dry state but became fragile in the wet state. On the contrary, the heat‐treated membranes were more flexible in the wet state than in the dry state. This change was explained by the turnaround of inner stress in the systems during the swelling process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Shear-induced crystallization of poly(phenylene sulfide)

The crystalline morphology of poly(phenylene sulfide) (PPS) isothermally crystallized from the melt under shear has been observed by polarized optical microscope (POM) equipped with a CSS450 hot-stage. The shish–kebab-like fibrillar crystal structure is formed at a higher shear rate or for a longer shear time, which is ascribed to the tight aggregation of numerous oriented nuclei in the direction of shear. The crystallization induction time of PPS decreases with the shear time, indicating that the shear accelerates the formation of stable crystal nuclei. Under shear, the increase of spherulite growth rate results from highly oriented chains. The melting behavior of shear-induced crystallized PPS performed by differential scanning calorimetry (DSC) shows multiple melting peaks. The lower melting peak corresponds to melting of imperfect crystal, and the degree of crystal perfection decreases as the shear rate increases. The higher melting peak is related to the orientation of molecular chains. These oriented molecular chains form the orientation nuclei which have higher thermal stability than the kebab-like lamellae that are developed later. A new model based on the above observation has been proposed to explain the mechanism of shish–kebab-like fibrillar crystal formation under shear flow.     

pH and salt responsive poly(N,N-dimethylaminoethyl methacrylate) cylindrical brushes and their quaternized derivatives

We present the synthesis and characterization of poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) cylindrical brushes, their pH responsiveness, and the corresponding quaternized analog, poly{[2-(methacryloyloxy)ethyl] trimethylammonium iodide} (PMETAI) brushes. PDMAEMA brushes were prepared by atom transfer radical polymerization (ATRP) using the grafting-from strategy. Initiating efficiencies of the ATRP processes were determined by cleaving the side-chains and gel permeation chromatography (GPC) analysis. Due to the slow initiation and steric hindrance, the initiating efficiency is only around 50%. The PDMAEMA brushes show worm-like structures and pH responsiveness, as proven by dynamic light scattering (DLS), atomic force microscopy (AFM), and cryogenic transmission electron microscopy (cryo-TEM) measurements. Strong cationic polyelectrolyte PMETAI brushes were produced by quaternization of the PDMAEMA brushes. AFM and cryo-TEM images showed similar worm-like morphologies for the PMETAI brushes. The PMETAI brushes collapsed in solution with high concentration of monovalent salt, as proven by DLS and AFM results.