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     

Modification of oil palm empty fruit bunches with maleic anhydride: The effect on the tensile and dimensional stability properties of empty fruit bunch/polypropylene composites

Oil palm empty fruit bunch (EFB)‐filled polypropylene (PP) composites were produced. The EFB filler was chemically modified with maleic anhydride (MAH). The effects of the filler size and chemical modification of EFBs on the tensile and dimensional stability properties of EFB–PP composites were studied. The composites with MAH‐treated EFBs showed higher tensile strengths than those with untreated EFBs. This was attributed to the enhanced compatibility between the MAH‐treated EFBs and PP matrix, as shown in a scanning electron microscopy study. Fourier transform infrared analysis showed evidence of C?C and C?O bonds from MAH at 1630 and 1730 cm^?1, respectively. The MAH‐treated PP composites showed lower water absorption and thickness swelling than those with untreated EFBs. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 827–835, 2003     

Effect of high polymerization temperature on the microstructure of isotactic polypropylene prepared using heterogeneous ticl4/mgcl2 catalysts

The effects of alkylaluminum and polymerization temperature on propylene polymerization without an external donor in the use of a TiCl₄–MgCl₂–diether(BMMF) catalyst were investigated. The results indicated that with increasing polymerization temperature the concentrations of [mmmm] of heptane‐insoluble poly(propylene) (PP) fraction increased. Crystallization analysis fractionation (CRYSTAF) results showed the fractions of different crystallization temperatures were changed according to various polymerization temperatures. The activity with Et₃Al as cocatalyst at 100°C was much lower than that at 70°C. However, the activity with i‐Bu₃Al at 100°C was as high as that at 70°C. The fraction of high‐crystallization temperature of PPs obtained with i‐Bu₃Al increased with increasing polymerization temperature, which was opposite to that with Et₃Al, thus implying that the copolymerization of propylene with the monomer arising from Et₃Al led to the lower crystallization ability of PPs obtained with Et₃Al. The terminal groups of PP suggested that the chain‐transfer reaction by β‐H abstraction was the main chain‐transfer reaction at 120°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3980–3986, 2003     

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     

Recycling of ethylene propylene diene monomer (EPDM) waste. III. Processability of EPDM rubber compound containing ground EPDM vulcanizates

The rheological behavior of ethylene propylene diene monomer (EPDM) compounds containing ground EPDM waste (W‐EPDM) of known composition was studied by using a Monsanto processability tester in a temperature range of 90–110°C and a shear rate range of 306.7–1533.24 s^?1. It is found that the shear viscosity decreases slightly with increasing W‐EPDM loading because of wall slip that results from the migration of lubricants from the W‐EPDM. The addition of W‐EPDM to raw EPDM results in a decreased die swell at all temperatures and shear rates. SEM photomicrographs of the EPDM extrudate surface show improved surface smoothness and reduced extrudate distortion when EPDM is blended with W‐EPDM. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2204–2215, 2003     

高矣物的特性对双水相相图和头孢氨苄及7-ADCA分配行为的影响

A series of ethylene oxide(EO)-propylene oxide (PO) random co-polymers (EOPO) were used to form aqueous two-phase systems (ATPS) with ammonium sulfate.Effects of EOPO′s properties on the phase separation behaviors and on the partition of cephalexin and 7-aminodesacetoxicephalosporanic acid(7-ADCA) in ATPS were investigated.Both the molar mass and molar ratio of EO to PO of EOPO could greatly influence partition behaviors of cephalexin and 7-ADCA as well as the binodal curve of ATPS. With the increase of molar mass of co-polymer or the decrease of molar ratio of EO to PO,the critical point of ATPS decreased,the binodal curve became more asymmetry,and both cephalexin and 7-ADCA followed the same tendency to partition into the polymer-poor bottom phase.The experimental results shows that it is feasible to partition cephalexin and 7-ADCA in either the polymer-rich top phase or the polymer-poor bottom phase by choosing a specific phase-forming EOPO.     

Use of a sodium ionomer as a compatibilizer in polypropylene/high‐barrier ethylene–vinyl alcohol copolymer blends: The processability of the blends and their physical properties

The effect of a sodium ionomer (ion.Na⁺) on the compatibility of polypropylene (PP)/high‐barrier ethylene–vinyl alcohol copolymer (EVOH) blends was studied in terms of the thermal, mechanical, and optical properties and morphology. The rheological behavior, tensile tests, and morphology of the binary blends showed that the miscibility of EVOH with PP was very poor. The miscibility of the polymers improved with the ionomer addition. In general, the ion.Na⁺ concentration did not alter the thermal behavior of the blends, but it did improve the ductility of the injection‐molded specimens. Scanning electron micrographs displayed better adhesion between the PP and EVOH phases in the samples with the ionomer. The mechanical improvement was better in the film samples than in the injection‐molded samples. A 90/10 (w/w) PP/EVOH film with 5% ion.Na⁺ and an 80/20 (w/w) PP/EVOH film with 10% ion.Na⁺ presented better global properties than the other blends studied. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1763–1770, 2004     

Isothermal crystallization kinetics and morphology development of isotactic polypropylene blends with atactic polypropylene

The crystallization kinetics and morphology development of pure isotactic polypropylene (iPP) homopolymer and iPP blended with atactic polypropylene (aPP) at different aPP contents and the isothermal crystallization temperatures were studied with differential scanning calorimetry, wide‐angle X‐ray diffraction, and polarized optical microscopy. The spherulitic morphologies of pure iPP and larger amounts of aPP for iPP blends showed the negative spherulite, whereas that of smaller amounts of aPP for the iPP blends showed a combination of positive and negative spherulites. This indicated that the morphology transition of the spherulite may have been due to changes the crystal forms of iPP in the iPP blends during crystallization. Therefore, with smaller amounts of aPP, the spherulitic density and overall crystallinity of the iPP blends increased with increasing aPP and presented a lower degree of perfection of the γ form coexisting with the α form of iPP during crystallization. However, with larger amounts of aPP, the spherulitic density and overall crystallinity of the iPP blends decreased and reduced the γ‐form crystals with increasing aPP. These results indicate that the aPP molecules hindered the nucleation rate and promoted the molecular motion and growth rate of iPP with smaller amounts of aPP and hindered both the nucleation rate and growth rate of iPP with larger amounts of aPP during isothermal crystallization. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1093–1104, 2007     

Synthesis and characterization of propylene‐α‐olefin random copolymers with isotactic propylene sequence. II. Propylene–hexene‐1 random copolymers

A series of novel hexene‐1–propylene random copolymers with isotactic sequence of propylene was synthesized with a MgCl₂‐supported Cr(acac)₃ catalyst. The molecular weight distribution of copolymers and homopolymers was considerably narrower than that of typical polyolefins produced by heterogeneous Ziegler–Natta catalysts. The crystallizability of the copolymers having a propylene‐unit content of more than 50 mol % drastically decreased with decreasing propylene‐unit content, and the copolymers with a propylene content of less than 50 mol % were completely amorphous. In the present novel type of random copolymers with crystallizable and noncrystallizable units, a single glass transition was observed between pure polypropylene and polyhexene‐1, and a major component was found to govern the final morphology and the mechanical characteristics. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2949–2954, 2004     

Mechanical property and morphology comparison between the two blends poly(propylene)/ethylene‐propylene‐diene monomer elastomer and poly(propylene)/maleic anhydride‐g‐ethylene‐propylene‐diene monomer

The comparison of the mechanical properties between poly(propylene)/ethylene‐propylene‐diene monomer elastomer (PP/EPDM) and poly(propylene)/maleic anhydride‐g‐ethylene‐propylene‐diene monomer [PP/MEPDM (MAH‐g‐EPDM)] showed that the latter blend has noticeably higher Izod impact strength but lower Young's modulus than the former one. Phase morphology of the two blends was examined by dynamic mechanical thermal analysis, indicating that the miscibility of PP/MEPDM was inferior to PP/EPDM. The poor miscibility of PP/MEPDM degrades the nucleation effectiveness of the elastomer on PP. The observations of the impact fracture mode of the two blends and the dispersion state of the elastomers, determined by scanning electron microscopy, showed that PP/EPDM fractured in a brittle mode, whereas PP/MEPDM in a ductile one, and that a finer dispersion of MEPDM was found in the blend PP/MEPDM. These observations indicate that the difference in the dispersion state of elastomer between PP/EPDM and PP/MEPDM results in different fracture modes, and thereby affects the toughness of the two blends. The finer dispersion of MEPDM in the blend of PP/MEPDM was attributed to the part cross‐linking of MEPDM resulting from the grafting reaction of EPDM with maleic anhydride (MAH) in the presence of dicumyl peroxide (DCP). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2486–2491, 2002