Biaxially Oriented Polypropylene (BOPP) Surface Modification by Nitrogen Atmospheric Pressure Glow Discharge (APGD) and by Air Corona

We compare two surface treatments of biaxially-oriented polypropylene (BOPP), which are carried out in the same dielectric barrier discharge (DBD) apparatus, namely air corona, and N₂ atmospheric pressure glow discharge (APGD). Changes in the surface energy and chemistry are investigated by contact angle measurements, by X-ray photoelectron spectroscopy (XPS) and by attenuated total reflectance infrared spectroscopy (ATR-FTIR). It is shown that N₂ APGD treatment leads to a higher surface energy than air corona treatment, and to the formation of mostly amine, amide, and hydroxyl functional groups at the polypropylene surface. Finally, hydrophobic recovery of the treated film is studied; for both treatment types, the increased surface energy is found to decay in a similar manner with increasing storage time after treatment.     

膨胀石墨微观孔结构的特点及其表征

膨胀石墨是一种疏松多孔的颗粒状新型碳材料［1，2］．由于在膨化过程中产生了丰富的孔结构，新鲜表面大为增加[3，4]，因此具有很好的吸附性能．探讨这种新材料孔结构的特征对于深入研究其吸附行为有重要意义．但目前尚没有对膨胀石墨孔结构进行系统研究的报导，本文采用低温N     

Crystallization of oriented smectic polypropylene I. Thermally induced crystallization

The crystallization induced by thermal treatments of smectic polypropylene fibres has been studied. Analysis was carried out detecting the density and X-ray diffractograms. Density and diffraction data disagree on two important aspects: the critical temperature necessary to activate the crystallization process, and the effects of annealing time on the growth process. The first point seems to suggest that the observed densification at the lower temperatures is related to phenomena differing from a crystallization process, while the observed effects of the annealing time can be explained by assuming that the anisotropy of the fibre structure induces anisotropy in the phase transition and growth process. On the other hand, density and diffraction data agree in indicating that the rate and degree of crystallization increase on increasing the crystallization temperature.     

Crystallization,melting and structure of polypropylene/poly(vinylidene-fluoride) blends

Blends were prepared from isotactic polypropylene (iPP) along with its b-nucleated form and poly(vinylidene-fluoride) (PVDF). Melting, and crystallization characteristics as well as structure of the blends were studied by polarized light microscopy (PLM) and differential scanning calorimetry. According to PLM studies, the phase structure of these blends is heterogeneous in the molten state. The temperature range of crystallization of PVDF during cooling is higher than that of iPP. PVDF has a strong α-nucleating effect on iPP. The crystallization of iPP starts on the surface of dispersed PVDF droplets and an α-transcrystalline layer forms on the surface of the crystalline PVDF phase. The iPP matrix crystallizes predominantly in a-form in spite of the presence of a highly active b-nucleating agent. This revised version was published online in August 2006 with corrections to the Cover Date.     

Copolymerization of propylene with higher α‐olefins in the presence of the syndiospecific catalyst i‐Pr(Cp)(9‐Flu)ZrCl2/MAO

The catalyst system i‐Pr(Cp)(9‐Flu)ZrCl₂/methylaluminoxane was used for the synthesis of random syndiotactic copolymers of propylene with 1‐hexene, 1‐dodecene, and 1‐octadecene as comonomers. An investigation of the microstructure by ¹³C NMR spectroscopy revealed that the stereoregularity of the copolymers decreased because of an increase in skipped insertions in the presence of the higher 1‐olefin. The melting temperature of the copolymers, as measured by differential scanning calorimetry (DSC), decreased linearly with increasing comonomer content independently of the comonomer nature. During the DSC heating cycle, an exothermic peak indicating a crystallization process was observed. The decrease in the crystallization temperature with higher 1‐olefin content, measured by crystallization analysis fractionation, indicated a small but significant dependence on the nature of the comonomer. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 128–140, 2002     

Characterization of the changes in the initial morphology for MgCl2-supported Ziegler-Natta polymerization catalysts

Recently considerable detail has become available on the initial morphology and the morphological changes that occur for silica based Cr catalysts for ethylene polymerization. These catalysts are produced as a dry powder and may be employed either in gas phase or in slurry processes. MgCl₂-supported Ziegler-Natta polymerization catalysts are often prepared and employed as slurries. They usually are never dried and thus few studies have employed the spectra of physical techniques common to the characterization of pore structure. In the current study, we have carefully removed the solvent for both ball-milled and precipitated MgCl₂-supported catalysts. These catalysts are characterized by physical sorption, mercury porosimetry, and electron microscopy both as prepared and during the initial stages of polymerization (to ～ 100 g of polymer/g of catalyst). We find that the initial catalyst may be represented by a complex agglomerate of small crystallites as contrasted with the branched pore network found in Cr/silica catalysts. As a result, it is concluded that the initial fragmentation of the MgCl₂ based systems is more uniform as contrasted with the progressive fragmentation of the silica-based system. This fragmentation mechanism facilitates the retention of greater polymer/catalyst surface during the initial stages of the polymerization. © 1992 John Wiley & Sons, Inc.     

Improved experimental characterization of crystallization kinetics

Polymer solidification occurring in many processes, like for instance injection molding, compression molding and extrusion, is a complex phenomenon, strongly influenced by the thermo-mechanical history experienced by the material during processing. From this point of view, characterization of polymer crystallization in the range of processing conditions, i.e. including high cooling rate, is of great technological and academic interest. Quiescent, non-isothermal crystallization kinetics of two polypropylene resins were investigated using a new method, based on fast cooling of thin samples with air/water sprays and optical detection of the crystallization phenomenon. The range of cooling rates attained in this experimental study is considerably larger than that achieved by traditional methods. Quiescent crystallization kinetics of the resins is also investigated by the means of DSC, operated under isothermal conditions with a limited degree of under-cooling and for constant cooling rates up to about 1 K s⁻¹. The results demonstrate the importance of performing fast cooling experiments to gather reliable crystallization kinetics data.     

Facile synthesis of oligo(4‐methoxyphenol) in water and evaluation of its efficiency in stabilization of polypropylene

A hindered polyphenol, oligo(4‐methoxyphenol), has been first successfully synthesized via a mild biocatalytic pathway using horseradish peroxidase as catalyst in water without any additive. Then the efficiency of oligo(4‐methoxyphenol) in stabilization of polypropylene (PP) was evaluated in terms of thermal analysis and accelerated aging test. It was observed that the apparent activation energy for thermal decomposition of PP/oligo(4‐methoxyphenol) calculated by Friedman's method is higher than that of virgin PP. Oligo(4‐methoxyphenol)‐stabilized PP maintains its tensile strength even after aging at 120°C for 800 hours. Oxidation induction time and onset oxidation temperature of PP/oligo(4‐methoxyphenol) are higher than both virgin PP and PP/4‐methoxyphenol, as well as PP stabilized with commercially available 6‐di‐tert‐buty‐4‐methylphenol or 1076. These results indicate that oligo(4‐methoxyphenol) can effectively improve the thermo‐oxidative resistance of PP. Noting that oligo(4‐methoxyphenol) is synthesized via enzymatic polymerization in water under mild condition with a facile procedure, oligo(4‐methoxyphenol) is thus proposed as a new efficiency and readily available antioxidant for PP.     

Synthesis of a novel hyperbranched and phosphorus‐containing charring‐foaming agent and its application in polypropylene

In this work, a novel hyperbranched and phosphorus‐containing triazine derivative (HPCFA) is synthesized. HPCFA is used as charring‐foaming agent and combined with ammonium polyphosphate (APP) as intumescent flame retardant to flame retard polypropylene (PP). PP/HPCFA/APP composite can achieve limited oxygen index value of 31% and pass UL 94V‐0 rating by addition of 20 wt% HPCFA/APP (1/2, w/w). Besides, HPCFA is compared with another hyperbranched charring‐foaming agent (HCFA). HPCFA and HCFA have similar chemical structure, and their only difference is that HPCFA has phosphorus‐containing unit in the main chain compared with HCFA. HPCFA/APP system exhibits superior flame retardancy compared with HCFA/APP system. Char residue analysis demonstrates that HPCFA/APP system can form denser and more compact char layer in comparison with that of HCFA/APP system.     

等离子体引发聚丙烯接技苯乙烯共聚物的合成及性能

将等离子体接枝技术用于聚丙烯接枝苯乙烯共聚物的合成．ＦＴ ＩＲ、ＳＥＭ及ＸＰＳ证明所得产物为接枝共聚物．研究了不同等离子体处理体系压强、处理功率，反应瓶不同直径、体积，不同接枝聚合反应时间、温度对接枝率的影响．利用接枝共聚物制备了硫酸钠型离子交换膜，并对其电性能进行了初步探讨．