Molecular weight distribution of polyethylene catalyzed by Ziegler–Natta catalyst supported on MgCl2 doped with AlCl3

Ti‐based Ziegler–Natta catalysts supported on MgCl₂ doped with AlCl₃ were prepared by the reaction of MgCl₂/AlCl₃–ethanol adduct with TiCl₄. No AlCl₃ crystallites were found in the AlCl₃‐doped catalysts by WAXD analysis, suggesting that AlCl₃/MgCl₂ solid solution was formed. The effect of doping on the catalyst performance in ethylene polymerization was investigated. The results showed that the catalysts based on AlCl₃‐doped MgCl₂ support exhibited a slightly higher activity than did the MgCl₂‐supported catalyst and the molecular weight distribution (MWD) of polyethylene (PE) markedly increased (from 10.8 to 47.9) with the increase of AlCl₃ content in catalysts. The changes in catalyst's active center distribution were studied based on nonlinear fitting of the polymer GPC curves by multiple Flory functions. It was found that increase of types of active centers by introducing AlCl₃ into the support should be responsible for the broadening of MWD of PE. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1768–1772, 2006     

Poly(p-tert-butoxycarbonyloxystyrene): a convenient precursor to p-hydroxystyrene resins

An efficient synthetic route to pure, high molecular weight poly(p-hydroxystyrene) is reported. The route involves synthesis of a new monomer, p-tert-butoxycarbonyloxystyrene, polymerization by radical initiation or by cationic initiation in liquid SO₂, followed by thermolysis or acidolysis of the tert-butoxycarbonyl protecting group. Porous, crosslinked resin beads containing the nucleophilic, phenol pendant group have been prepared in a similar fashion from the precursor terpolymer of p-tert-butoxycarbonyloxystyrene, styrene and divinylbenzene. The utility of this resin for solid-phase synthesis has been demonstrated.     

Physical properties of polycaproamide/cationic dyeable poly(ethylene terephthalate) polyblended fibers

Polycaproamide (PCA) and cationic dyeable poly(ethylene terephthalate) (CDP) polymers were blended mechanically (in ratios of 75/25, 50/50, and 25/75) in a melt twin‐screw extruder to prepare three PCA/CDP polyblended materials. The blends of PCA and CDP were spun into fibers. The molar ratio of dimethyl 5‐sulfoisophthalate sodium salt for CDP was 2%. This study investigated the physical properties of PCA/CDP polyblended fibers with nuclear magnetic resonance, gel permeation chromatography, gas chromatography, potentiometer, differential scanning calorimetry (DSC), thermogravimetric analysis, scanning electron microscopy (SEM), extension stress–strain measurements, density gradient analysis, and rheometry. The experimental results of DSC proved that PCA and CDP formed an immiscible system. In an SEM image of a 50/50 PCA/CDP blend, the morphological aggregation of a larger size, from 3 to 5 μm in diameter, was observed. The rheological behavior of the PCA/CDP polyblended materials exhibited negative‐deviation blends, and the 50/50 blend of the PCA/CDP polyblended fibers showed a minimum tenacity value. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1710–1715, 2004     

Heterogeneously assisted oxidation of adsorbates from carbonmonoxide, methanol and ethanol by hydrogen peroxide solutions on platinum electrodes in sulphuric acid

The influence of hydrogen peroxide on the adsorption and oxidation of carbon monoxide, methanol and ethanol adlayers on porous Pt electrodes were studied in 2 M sulphuric acid solution by means of cyclic voltammetry and differential electrochemical mass spectrometry (DEMS). The oxidation of adsorbed species is observed at electrode potentials far less negative than those required for electrochemical adsorbate oxidation. The oxidation by H₂O₂ is dependent on its concentration in solution, as well as on the adsorbates and their coverages. In all cases the isolated adlayers are oxidised by dissolved H₂O₂. However, the presence of H₂O₂ during adsorption partially inhibits adlayer formation from CH₃OH and C₂H₅OH, but avoids almost completely the adsorption of carbon monoxide. The removal of the residues from the surface by dissolved hydrogen peroxide probably occurs through O_ad species formed during the heterogeneous decomposition reaction of H₂O₂ on Pt.     

Impregnation of X Zeolite with Alkaline Hydroxide During the Synthesis

Enhancement of the basic properties of the X zeolite with FAU framework has been carried out during synthesis, without further treatment such as ion-exchange or impregnation. Control of the washing stage enables retention of the optimum amount of alkaline hydroxides, which increases the basic catalytic activity of X zeolite in the alkylation of toluene. This alkaline hydroxides neither affect the FAU framework nor the silicon/aluminium molar ratio of the X zeolite. The optimum (Na + K)/Al molar ratio of the improved catalyst was 1.06 corresponding to a washing volume of 200 mL. This X zeolite presented better catalytic activity than a cesium-zeolite prepared by ion-exchange. The presence of hydroxysodalite impurity in the X zeolite increased the amount of impregnated alkaline hydroxides but not the catalytic activity. The present study shows that it is possible to increase the basic properties of the X zeolite directly in the synthesis process.     

Electrooxidation of methanol at platinum–ruthenium catalysts prepared from colloidal precursors: Atomic composition and temperature effects

The electrocatalytic oxidation of methanol was investigated on PtRu electrodes of different atomic compositions at several temperatures (from 25 to 110 °C). Very active catalyst nanoparticles supported on active carbon (Vulcan XC 72) were obtained using the colloidal synthesis developed by Bönnemann et al. [11], allowing easy variation of the atomic composition. These electrocatalysts were characterized by TEM, EDX and XRD; results indicate that they consist of platinum nanoparticles decorated by ruthenium. Methanol oxidation was studied as a function of composition, temperature and methanol concentration. Two effects were investigated: the effect of the working temperature and the effect of the atomic composition. It appeared that for lower methanol electrooxidation overvoltages, the best catalysts are ruthenium-rich, whereas at higher overvoltages the best one is the Pt + Ru (80:20)/C composition, irrespective of the working temperature, either in half-cell or in a single DMFC.     

Syndiotactic Polystyrene/Organoclay Nanocomposites: Synthesis via In Situ Coordination‐Insertion Polymerization and Preliminary Characterization

Summary: Syndiotactic polystyrene (sPS)/organophilic clay nanocomposites were obtained by in situ coordination‐insertion polymerization of styrene. Two cationic surfactants (alkylammonium and alkylphosphonium) were used for the intercalation of montmorillonite (MMT). For each organically modified clay, three protocols were performed using an MAO‐activated hemi‐metallocene catalyst, in order to compare the influence of experimental conditions on the composite microstructure and on its thermal stability. The microstructures of nanocomposites were investigated by wide angle X‐ray scattering and DSC. Partially exfoliated or intercalated materials were obtained in all cases and a decrease of crystallinity is observed. Thermal properties were also studied by DSC and thermogravimetric analysis. The presence of clay does not have a strong influence on the sPS thermal transitions but the thermal decomposition process of the material was slowed down in the presence of few organoclay percents, particularly in the degradation beginning. The influence of these two organically modified clays on the thermal stability of the material is discussed.

Gel and suspension formed from the combination of cloisite with toluene (left) and styrene (right), respectively.     

Synthesis of 2‐monoglycerides by alcoholysis of palm oil and tuna oil using immobilized lipases

Commercial immobilized lipases were used for the synthesis of 2‐monoglycerides (2‐MG) by alcoholysis of palm and tuna oils with ethanol in organic solvents. Several parameters were studied, i.e., the type of immobilized lipases, water activity, type of solvents and temperatures. The optimum conditions for alcoholysis of tuna oil were at a water activity of 0.43 and a temperature of 60 °C in methyl‐tert‐butyl ether for ～12 h. Although immobilized lipase preparations from Pseudomonas sp. and Candida antarctica fraction B are not 1, 3‐regiospecific enzymes, they were considered to be more suitable for the production of 2‐MG by the alcoholysis of tuna oil than the 1, 3‐regiospecific lipases (Lipozyme RM IM from Rhizomucor miehei and lipase D from Rhizopus delemar). With Pseudomonas sp. lipase a yield of up to 81% 2‐MG containing 80% PUFA (poly‐unsaturated fatty acids) from tuna oil was achieved. The optimum conditions for alcoholysis of palm oil were similar as these of tuna oil alcoholysis. However, lipase D immobilized on Accurel EP100 was used as catalyst at 40 °C with shorter reaction times (<12 h). This lead to a yield of ～60% 2‐MG containing 55.0‐55.7% oleic acid and 18.7‐21.0% linoleic acid.     

Curing and pyrolysis of cresol novolac epoxy resins containing [2‐(6‐oxido‐6H‐dibenz(c,e)(1,2)oxaphosphorin‐6‐yl)‐1,4‐naphthalenediol]

This study investigates the curing kinetics, thermal properties and decomposition kinetics of cresol novolac epoxy (CNE) with two curing agents, 2‐(6‐oxido‐6H dibenz(c,e)(1,2) oxaphosphorin‐6‐yl)‐1,4‐benzenediol (ODOPN), and phenol novolac (PN). In comparison with the conventional PN system, introducing ODOPN, a phosphorus‐containing bulky pendant group, into CNE increases T_g by 33°C, char yield from 30% to 38%, and LOI from 22 to 31. The DSC curing study reveals that the E_a of the CNE/ODOPN epoxy can be obtained by Kissinger's method. The resulting E_a values indicate that the catalytic effect of EMI is insignificant on CNE/ODOPN but is marked on CNE/PN, whose E_a was reduced from 131.5 to 75.6 KJ/mole. This result may be caused by the fact that the symmetric diol attached to the 1 and 4 positions of the naphthalene ring in ODOPN sets up a steadily resonating structure and inhibits the catalytic action. Further investigating the conversion ratio with curing temperature yielded experimental data that agreed closely with Kaiser's model. The orders of the autocatalyzed reaction, m, and the crosslinking reaction, n, are close to 0.5 and 1.0, respectively, independently of the scan rate. Finally, the TGA decomposition study by Ozawa's method demonstrates that the mean E_a declines with the phosphorus content, because the easy decomposition of the phosphorus compound in the initiation stage facilitates the formation of an insulating layer. However, results in this study further reveal an increasing tendency for E_a with decomposition conversion for an ODOPN/PN mixture with the ODOPN content of over 50%, probably because of the retardation of gas diffusion by the insulating layer of phosphorus compound.