EFFECTS OF COUPLING AGENTS ON THE CRYSTALLIZATION BEHAVIOR OF PP/T-ZnOw COMPOSITES

The objectives of this paper are to understand the crystallization behavior of polypropylene(PP)composites with surface modified tetra-needle-shaped zinc oxide whisker(T-ZnOw).T-ZnOw was surface modified with different coupling agents,such as silane coupling agents(KH-550,KH-560)and titanate coupling agent(NDZ-105),in order to improve the compatibility between PP and T-ZnOw.DSC and POM were used to characterize the melt and crystallization behavior and the crystalline structures of the composites,respectively.The results show that the surface modified T-ZnOw acts as a nucleating agent of PP crystallization,depending on the coupling agent used for modification.KH-550 and KH-560 have more apparent role in improving the interfacial interaction than NDZ-105 and induce PP crystallization at higher temperature and with smaller spherulites size.The results also suggest that the crystallization behavior depends on not only the content of coupling agent,but also the content of the surface modified T-ZnOw used in the composites.     

Copolyesterification between poly(butylene terephthalate), terephthalic acid and hydroquinone diacetate: a kinetic analysis

The kinetics of liquid crystalline copolyester synthesis via melt transesterification between poly(butylene terephthalate) (PBT), terephthalic acid (TA) and hydroquinone diacetate (HQDA) is examined. Two different copolyester compositions PBT30/(HQDA+TA) 70 and PBT 50/(HQDA+TA) 50 mol% ratio were synthesized. The ratio of HQDA to TA was kept constant for all the reactions.The copolyesters were synthesized via melt polycondensation route at 265°C, 275°C and 285°C using two different transesterification catalysts, zinc acetate and dibutyl tin oxide. A key postulation assumed in this work is that the reaction originates between TA and HQDA to form a dimer which slices PBT chain. The copolyesterification rate constant for a system containing butylene glycol a more nonpolar moiety compared to ethylene glycol in poly(ethylene terephthalate) has been determined. The activation energy values for the different copolymer systems has also been determined. The rate constants for the uncatalyzed and catalyzed copolyesterification reaction and the activation energy values for the reaction have been determined.     

新型尼龙214,414,614,814,1014和1214的合成与表征

用熔融缩聚法基于十四碳二酸合成了一系列偶偶尼龙，包括尼龙2 14，4 14， 6 14，8 14，10 14，12 14。用红外光谱、元素分析、核磁共振、差示扫描热分析 、热失重分析、热机械分析、粘度法对合成尼龙的结构与性能进行了表征。同时还 初步研究了尼龙12 14的物理性能，发现其物理性能介于尼龙66和聚乙烯之间。     

Preparation and Characterization of Microencapsulated Hexadecane Used for Thermal Energy Storage

Polyurea microcapsules about 2.5μm in diameter containing phase change material for thermal energy storage application were synthesized and characterized by interfacial polycondensation method with toluene-2,4-diisocyanate and ethylenediamine as monomers in an emulsion system. Hexadecane was used as a phase change material and OP, which is nonionic surfactant, and used as an emulsifier. The chemical structure and thermal behavior of the microcapsules were investigated by FTIR and thermal analysis respectively. The results show encapsulated hexadecane has a good potential as a solar energy storage material.     

Novel random poly(propylene isophthalate/adipate) copolyesters: Synthesis and characterization

Poly(propylene adipate) (PPA) and poly(propylene isophthalate/adipate) (PPI-PPA) random copolymers of various compositions were synthesized in bulk and characterized in terms of chemical structure and molecular weight. Furthermore, the thermal behavior was examined by thermogravimetric analysis and differential scanning calorimetry. All the polymers showed a good thermal stability. At room temperature they appeared as semicrystalline materials, except the copolymers containing 20 and 30 mol% of PI units: the main effect of copolymerization was a lowering in the amount of crystallinity and a decrease of melting temperature with respect to homopolymers. The crystalline phase of PPI and PPA was evidenced at high content of propylene isophthalate or propylene adipate units, respectively. Amorphous samples were obtained after melt quenching and an increment of T_g as the content of PI units is increased was observed. This behavior was explained as due to the stiff phenylene groups in the polymeric chain. The Wood equation was found to describe well T_g-composition data. Lastly, the presence of a rigid-amorphous phase was evidenced in the copolymers, differently from PPA homopolymer.     

Direct electrochemistry of recombinant tobacco peroxidase on gold

Direct electron transfer (DET) reactions of recombinant tobacco peroxidase (rTOP), namely direct electroreduction of Compound I/Compound II and heme Fe^3+/2+ conversion, were studied on gold electrodes. rTOP of wild type, non-glycosylated, was produced using an Escherichia coli expression system. At pH 5.0, the redox potential for direct electrochemical transformation of the Fe^3+/2+ of the peroxidase heme was −143 mV vs. AgAgCl, and 0.26 ± 0.07 pmol of the adsorbed rTOP were in DET contact with the gold electrode. The total amount of the adsorbed rTOP estimated from QCM data was 53 ± 5 pmol/cm² or 1.67 pmol when referred to the surface area of the electrodes used for electrochemical measurements. Of 1.67 pmol of adsorbed rTOP, only 0.76 pmol were catalytically active. DET between Au and the enzyme was also studied in the reaction of the bioelectrocatalytic reduction of H₂O₂ by cyclic voltammetry and amperometric detection of H₂O₂ at +50 mV with rTOP-modified Au electrodes placed in a wall-jet flow-through electrochemical cell. Maximal bioelectrocatalytic current response of the rTOP-modified gold electrodes to H₂O₂ was observed at pH 5.0 and stemmed from its bioelectrocatalytic reduction based on DET between Au and the active site of rTOP. Kinetic analysis of the DET reactions gave 52% of the adsorbed rTOP molecules active in DET reactions (0.4 pmol of adsorbed catalytically active rTOP, correspondingly), which correlated well with the non-catalytic-voltammetry data. DET was characterised by a heterogeneous ET rate constant of 13.2 s⁻¹, if one takes into account the QCM data, and 19.6 s⁻¹, if the amount of rTOP estimated from the data on DET transformation of Fe^3+/2+ couple of rTOP is considered. The sensitivity for H₂O₂ obtained for the rTOP-modified Au electrodes was 0.7 ± 0.1 A M⁻¹ cm⁻². These are the first ever-reported data on DET reactions of anionic plant peroxidases on bare gold electrodes.     

Preparation and characterization of new thermally stable and optically active poly(ester‐imide)s by direct polycondensation with thionyl chloride in pyridine

4,4′‐hexafluoroisopropylidene‐2,2‐bis‐(phthalic acid anhydride) (1) was reacted with L ‐methionine (2) in acetic acid and the resulting N,N′–(4,4′‐hexafluoroisopropylidenediphthaloyl)‐bis‐L ‐methionine (4) was obtained in high yield. The direct polycondensation reaction of this diacid with several aromatic diols such as bisphenol A (5a), phenolphthalein (5b), 1,4‐dihydroxybenzene (5c), 4,4′‐dihydroxydiphenyl sulfide (5d), 4,6‐dihydroxypyrimidine (5e), 4,4′‐dihydroxydiphenyl sulfone (5f) and 2,4′‐dihydroxyacetophenone (5g) was carried out in a system of thionyl chloride and pyridine. Expecting that the reaction with thionyl chloride in pyridine might involve alternative intermediates different from an acyl chloride, the polycondensation at a higher temperature favorable for the reaction of the expected intermediate with nucleophiles was attempted, and a highly thermally stable poly(ester‐imide) was obtained by carrying out the reaction at 80°C. All of the above polymers were fully characterized by ¹H‐NMR, ¹⁹F‐NMR FT‐IR spectroscopy, elemental analysis and specific rotation. Some structural characterization and physical properties of these optically active poly(ester‐ imide)s are reported. Copyright © 2006 John Wiley & Sons, Ltd.     

Solid-state polyamidation of hexamethylenediammonium adipate. II. The influence of acid catalysts

Loss of diamine and distinct transition phenomena from the solid to the melt state restrain solid-state polymerization (SSP) of nylon salts from industrial application. To depress these phenomena temperatures well below the melting point of the starting material are employed, resulting however in low reaction rates. The need to use catalysts arises and accordingly in this study hexamethylenediammonium adipate (HMA) particles were polymerized containing a strictly controlled amount of uniformly distributed catalyst. The catalysts included boric, sulphuric, and phosphoric acids with boric acid being the most effective in accelerating the reaction while eliminating the tendency to agglomeration. In general, catalyst concentration up to a critical value plays a considerable role in the overall behavior. Furthermore, in agreement with non catalytic processes, the reaction temperature remains an influential parameter. © 1994 John Wiley & Sons, Inc.