Nanosized silica‐supported metallocene/MAO catalyst for propylene polymerization

A nanosized silica particle was used as the support to prepare an Et[Ind]₂ZrCl₂/MAO catalyst for propylene polymerization of polypropylene. The catalyst and the polymer produced were characterized with nitrogen adsorption, ICP, DSC, SEM, TEM, XRD, solution viscometer, ¹³C NMR and optical microscopy. The effects of polymerization temperature and [Al]/[Zr] ratio on catalyst activity and polymer melting point were investigated. Under identical reaction conditions, nanosized catalyst exhibited better polymerization activity than the microsized catalyst (e.g., the former had 64% higher activity than the latter at the optimum polymerization temperature (50°C) and [Al]/[Zr] = 570). DSC results indicated that polymer melting point increased with the increase of [Al]/[Zr] ratio and with the decrease of polymerization temperature. XRD results showed that the percentage of γ crystals increased with decreasing [Al]/[Zr] ratio. Electron microscopic results showed that the polymer particle size increased with increasing polymerization temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2573–2580, 2006     

Synthesis and properties of polystyrene‐b‐poly(ethylene oxide)‐b‐polystyrene triblock copolymers

A series of well‐defined and property‐controlled polystyrene (PS)‐b‐poly(ethylene oxide) (PEO)‐b‐polystyrene (PS) triblock copolymers were synthesized by atom‐transfer radical polymerization, using 2‐bromo‐propionate‐end‐group PEO 2000 as macroinitiatators. The structure of triblock copolymers was confirmed by ¹H‐NMR and GPC. The relationship between some properties and molecular weight of copolymers was studied. It was found that glass‐transition temperature (T_g) of copolymers gradually rose and crystallinity of copolymers regularly dropped when molecular weight of copolymers increased. The copolymers showed to be amphiphilic. Stable emulsions could form in water layer of copolymer–toluene–water system and the emulsifying abilities of copolymers slightly decreased when molecular weight of copolymers increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 727–730, 2006     

PSA performances and viscoelastic properties of SIS‐based PSA blends with H‐DCPD tackifiers

Hotmelt pressure sensitive adhesives (PSAs) usually contain styrenic block copolymers like styrene–isoprene–styrene (SIS), SBS, SEBS, tackifier, oil, and additives. These block copolymers individually reveal no tack. Therefore, a tackifier is a low molecular weight material with high glass transition temperature (T_g), and imparts the tacky property to PSA. The SIS block copolymer with different diblocks was blended with hydrogenated dicyclopentadiene (H‐DCPD tackifier), which has three kinds of T_g. PSA performance was evaluated by probe tack, peel strength, and shear adhesion failure temperature. PSA is a viscoelastic material, so that its performance is significantly related to the viscoelastic properties of PSAs. We tested the viscoelastic properties by dynamic mechanical analysis and the thermal properties by differential scanning calorimeter to investigate the relation between viscoelastic properties and PSA performance. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 102: 2839–2846, 2006     

Experimental Study on the Hydrodynamics and Mass Transfer Characteristics of Ultrasonic Loop Airlift Reactor

The promoting effect of ultrasonic wave on the hydrodynamics and mass transfer characteristics of the loop airlift reactor was studied. The gas holdup, liquid circulation velocity, mixing time and overall volumetric mass transfer coefficient were examined and compared, with and without ultrasonic wave in the reactor. The experimental results show that ultrasound has almost no notable effect on the gas holdup, but has a tendency to decrease gradually the liquid circulation velocity and increase the overall volumetric mass transfer coefficient; and the effect on the mixing time is relatively complex. At low superficial gas velocity, the low powered ultrasound promotes the radial mixing of fluid; with the ultrasonic power increasing, ultrasonic vibration obstructs the axial mixing of fluid. Moreover, the effect of ultrasonic wave on the mixing time gradually decreases with the increase in the superficial gas velocity. Therefore there exists an optimal ultrasonic power for hydrodynamics and mass transfer. Correlations were also proposed for the hydrodynamics and mass transfer characteristics of the reactor.     

Synthesis and properties of poly(aryl ether sulfone ether ketone ketone) (PESEKK)

4,4′‐bis(Phenoxy)diphenyl sulfone (DPODPS) was synthesized by reaction of phenol with bis(4‐chlorophenyl) sulfone in tetramethylene sulfone in the presence of NaOH. Two poly(aryl ether sulfone ether ketone ketone)s (PESKKs) with high molecular weight were prepared by low temperature solution polycondensation of DPODPS and terephthaloyl chloride (TPC) or isophthaloyl chloride (IPC), respectively, in 1,2‐dichloroethane and in the presence of aluminum chloride (AlCl₃) and N‐methylpyrrolidone (NMP). The resulting polymers were characterized by various analytical techniques, such as FT‐IR, ¹H‐NMR, DSC, TG, and WAXD. The results show that the T_g and T_d of PESEKKs are much higher, but its T_m is lower than those of PEKK. The other results indicate that PESEKKs exhibit excellent thermostabilities at 300 ± 10°C. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 489–493, 2005     

Application of essential work of fracture concept to toughness characterization of high‐density polyethylene

Deformation and fracture toughness of high‐density polyethylene (HDPE) in plane‐stress tension was studied using the concept of essential work of fracture (EWF). Strain range for necking was determined from uniaxial tensile test, and was used to explain the deformation transition for 2‐staged crack growth in double‐edge‐notched tensile test. Through work‐partitioning, EWF values for HDPE were determined for each stage of the crack growth. Appropriateness of these EWF values to represent the material toughness is discussed. The study concludes that the EWF values for ductile polymers like HDPE may not be constant, but vary with the deformation behaviour involved in the crack growth process. POLYM. ENG. SCI., 47:1327–1337, 2007. © 2007 Society of Plastics Engineers     

Synthesis of polystyrene/poly(butyl acrylate) core–shell latex and its surface morphology

A polystyrene (PS)/poly(butyl acrylate) (PBA) composite emulsion was produced by seeded emulsion polymerization of butyl acrylate (BA) with PS seed particles which were prepared by emulsifier‐free polymerization of styrene with potassium persulfate (KPS) under a nitrogen atmosphere at 70°C for 24 h with stirring at 60 rpm and swelled with the BA monomer in an ethanol/water medium. The structure of the PS/PBA composite particles was confirmed by the presence of the characteristic absorption band attributed to PS and PBA from FTIR spectra. The particles for pure PS and PS/PBA with a low content of the BA monomer were almost spherical and regular. As the BA monomer content was increased, the particle size of the PS/PBA composite particles became larger, and more golf ball‐like particles were produced. The surface morphology of the PS/PBA composite particles was investigated by AFM and SEM. The T_g's attributed to PS and PBA in the PS/PBA composite particles were found at 110 and ?49°C, respectively. The thermal degradation of the pure PS and PS/PBA composite particles occurred in one and two steps, respectively. With an increasing amount of PBA, the initial thermal decomposition temperature increased. On the contrary the residual weight at 450°C decreased with an increasing amount of PBA. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 595–601, 2003     

Preparation and swelling behavior of biodegradable hydrogels based on α,β‐poly(N‐2‐hydroxyethyl‐DL‐aspartamide)

Biodegradable polymers and the hydrogels have been increasingly applied in a variety of biomedical fields and pharmaceutics. α,β‐Poly(N‐2‐hydroxyethyl‐DL ‐aspartamide), PHEA, one of poly(amino acid)s with hydroxyethyl pendants, are known to be biodegradable and biocompatible, and has been studied as an useful biomaterial, especially for drug delivery, via appropriate structural modification. In this work, hydrogels based on PHEA were prepared by two‐step reaction, that is, the crosslinking of polysuccinimide, the precursor polymer, with oligomeric PEG or PEI‐diamines and the following nucleophilic ring‐opening reaction by ethanolamine. Soft hydrogels possessing varying degrees of gel strength could be prepared easily, depending on the amount of different crosslinking reagents. The swelling degrees, which were in the range of 10–40 g–water/dry gel, increased somewhat at higher temperature, and also at alkaline pH of aqueous solution. A typical hydrogel remained almost unchanged for 1 week, at 37°C in phosphate buffer of pH 7.4, and then seemed to degrade slowly as time. A porous scaffold could be fabricated by the freeze drying of water‐swollen gel. The PHEA‐based hydrogels have potential for useful biomaterial applications including current drug delivery system. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3741–3746, 2003     

Influence of post‐extrusion parameters on the final morphology of polystyrene/high density polyethylene blends

The deformation of the dispersed phase in polystyrene/high density polyethylene (PS/HDPE) blends produced by ribbon extrusion was studied numerically and experimentally. A mathematical model for the deformation of the dispersed phase in ribbon extrusion processing of polymer blends was developed assuming uniaxial deformation of the ribbon and the equilibrium shapes of the dispersed particles with a pressure balance over a drop. Simulated morphologies as function of the post‐extrusion parameters were obtained and compared with experiments. The analysis of the ribbon extrusion process showed that parameters such as draw ratio (DR) and ribbon‐water contact length (X) significantly influence the ribbon dimensions, the extensional stress, and the stretching force. The results also showed that deformation and coalescence of the dispersed phase in the ribbon extrusion processing of polymer blends increase at higher DR and/or lower X values. The comparison between the model and the experimental morphologies of PS/HDPE produced a good agreement.     

Preparation and characterization of maleic anhydride‐g‐polypropylene/diamine‐modified clay nanocomposites

Polypropylene (PP)/montmorillonite (MMT) nanocomposites were prepared by compounding maleic anhydride‐g‐polypropylene (MAPP) with MMT modified with α,ω‐diaminododecane. Structural characterization confirmed the formation of characteristic amide linkages and the intercalation of MAPP between the silicate layers. In particular, X‐ray diffraction patterns of the modified clay and MAPP/MMT composites showed 001 basal spacing enlargement as much as 1.49 nm. Thermogravimetric analysis revealed that the thermal decomposition of the composite took place at a slightly higher temperature than that of MAPP. The heat of fusion of the MAPP phase decreased, indicating that the crystallization of MAPP was suppressed by the clay layers. PP/MAPP/MMT composites showed a 20–35% higher tensile modulus and tensile strength compared to those corresponding to PP/MAPP. However, the elongation at break decreased drastically, even when the content of MMT was as low as 1.25–5 wt %. The relatively short chain length and loop structure of MAPP bound to the clay layers made the penetration of MAPP molecules into the PP homopolymer phase implausible and is thought to be responsible for the decreased elongation at break. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 307–311, 2005