Novel catalyst systems based on Ni(II), Ti(IV), and Cr(III) complexes for oligo-and polymerization of ethylene

The complex of Brookhart Ni(α-diimine)Cl2 (1) (α-diimine = 1,4-bis(2,6- diisopropylphenyl)-acenaphthenediimine) has been characterized after impregnation on silica (S1) and MAO-modified silicas (4.0, 8.0 and 23.0 wts.% Al/SiO2 called S2, S3 and S4, respectively). The treatment of these heterogeneous systems with MAO produces some active catalysts for the polymerization of the ethylene. A high catalytic activity has been gotten while using the system supported 1/S3 (196 kg of PE/mol[Ni].h.atm; toluene, Al/Ni = 1000, 30ºC, 60 min and atmospheric pressure of ethylene). The effects of polymerization conditions have been tested with the catalyst supported in S2 and the best catalytic activity has been gotten with solvent hexane, MAO as cocatalyst, molar ratio Al/Ni of 1000 and to the temperature of 30°C (285 kg of PE/mol[Ni].h.atm). When the reaction has been driven according to the in situ methodology, the activity practically doubled and polymers showed some similar properties. Polymers products by the supported catalysts showed the absence of melting fusion, results similar to those gotten with the homogeneous systems by DSC analysis. But then, polymers gotten with the transplanted system present according to the GPC’s curves the polydispersity (MwD) varies between 1.7 and 7.0. A polyethylene blend (BPE/LPE) was prepared using the complex Ni(α-diimine)Cl2 (1) (α-diimine = 1,4-bis(2,6-diisopropylphenyl)-acenaphthenediimine) and {TpMs*}TiCl3 (2) (TpMs* = hydridobis(3-mesitylpyrazol-1-yl)(5-mesitylpyrazol-1-yl)) supported in situ on MAO-modified silica (4.0 wts. -% Al/SiO2, S2). Reactions of polymerization of ethylene have been executed in the toluene in two different temperatures (0 and 30°C), varying the molars fraction of nickel (xNi), and using MAO as external cocatalyst. To all temperatures, the activities show a linear variation tendency with xNi and indicate the absence of the effect synergic between the species of nickel and the titanium. The maximum of activity have been found at 0°C. The melting temperature for the blends of polyethylene produced at 0 °C decrease whereas xNi increases indicating a good compatibility between phases of the polyethylene gotten with the two catalysts. The melting temperature for the blends of polyethylene showed be depend on the order according to which catalysts have been supported on the MAO-modified silica. The initial immobilization of 1 on the support (2/1/S2) product of polymers with a melting temperature (Tm) lower to the one of the polymer gotten when the titanium has been supported inicially (1/2/S2). The observation of polyethylenes gotten with the two systems (2/1/S2 and 1/2/S2) by scanning electron microscopy (SEM) showed the spherical polymer formation showing that the spherical morphology of the support to been reproduced. Are described the synthesis, the characterization and the catalytic properties for the oligomerization of the ethylene of four organometallics compounds of CrIII with ligands ([bis[2-(3,5-dimethyl-1-pyrazolyl)ethyl]amine] chromium (III) chloride (3a), [bis[2-(3,5- dimethyl-l-pyrazolyl)ethyl]benzylamine] chromium (III) chloride (3b), [bis[2-(3,5-dimethyl-lpyrazolyl) ethyl]ether] chromiun(III)chloride (3c), [bis[2-(3-phenyl-lpyrazolyl) ethyl]ether]chromiun(III)chloride (3d)). In relation of the oligomerization, at exception made of the compounds 3a, all complex of the chromium showed be active after activation with MAO and the TOF gotten have one effect differentiated to those formed with CrCl3(thf)3. The coordination of a tridentate ligand on the metallic center doesn't provoke any considerable changes on the formation of the C4 and C6, but the amount of C8 are decrease and the C10 and C12+ have increased. The Polymers produced by the catalyst 3a to 3 and 20 bar of ethylene have, according to analyses by DSC, the temperatures of fusion of 133,8 and 136ºC respectively. It indicates that in the two cases the production of high density polyethylene. The molar mass, gotten by GPC, is 46647 g/mols with MwD = 2,4 (3 bar). The system 3c/MAO showed values of TOF, activity and selectivity to different α-olefins according to the pressure of ethylene uses. Himself that shown a big sensibility to the concentration of ethylene solubilized.

Effect of Flasking and Polymerization Techniques on Tooth Movement in Complete Denture Processing

Purpose: The purpose of this study was to compare the artificial tooth positional changes following the flasking and polymerization of complete dentures by a combination of two flasking methods and two polymerization techniques using computer graphic measurements.Materials and Methods: Four groups of waxed complete dentures (n = 10) were invested and polymerized using the following techniques: (1) adding a second investment layer of gypsum and conventional water bath polymerization (Control), (2) adding a second investment layer of gypsum and polymerization with microwave energy (Gyp-micro), (3) adding a second investment layer of silicone (Zetalabor) and conventional polymerization (Silwater), and (4) adding a second investment layer of silicone and polymerization with microwave energy (Silmicro). For each specimen, six segments of interdental distances (A to F) were measured to determine the artificial tooth positions in the waxed and polymerized stages using software program AutoCad R14. The mean values of the changes were statistically compared by univariate ANOVA with Tukey post-hoc test at 5% significance.Results: There were no significant differences among the four groups, except for segment D of the Silmicro group (-0.004 +/- 0.032 cm) in relation to the Gypwater group (0.044 +/- 0.031 cm) (p < 0.05), which presented, repectively, expansion and shrinkage after polymerization.Conclusions: Within the limitations of this study, it was concluded that although the differences were not statistically significant, the use of a silicone investment layer when flasking complete dentures resulted in the least positional changes of the artificial teeth regardless of the polymerization technique.

Effect of the Insertion and Polymerization Technique in Composite Resin Restorations: Analysis of Marginal Gap by Atomic Force Microscopy

This in vitro study evaluated the marginal gap at the composite tooth/resin interface in class V cavities under the influence of two insertion techniques and a curing system by means of atomic force microscopy (AFM). Forty enamel and dentin cavities were prepared on the buccal surface in bovine teeth with quadratic forms measuring 2 mm X 2 mm and depth of 1.5 mm. The teeth were then divided into four groups: group A, 10 cavities were restored in one increment, light cured by halogen light; group B, 10 cavities filled with bulk filling, light cured by the light emitting diodes (LED); group C, 10 cavities were restored by the incremental technique, light cured by halogen light; group D, 10 cavities were restored by the incremental technique, light cured by the LED. The teeth underwent the polishing procedure and were analyzed by AFM for tooth/restoration interface evaluation. The data were compared between groups using the nonparametric Kruskall-Wallis and Mann-Whitney tests (p < 0.05). The results showed a statistically significant difference between groups A and B and groups A and C. It was concluded that no insertion and polymerization technique was able to completely seal the cavity.

Leachability of degradation products from hard chairside reline resins in artificial saliva: effect of water-bath post-polymerization treatment

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Influence of different light sources and photo-activation methods on degree of conversion and polymerization shrinkage of a nanocomposite resin

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Purification and Characterization of Two Extracellular Xylanases from Penicillium sclerotiorum: A Novel Acidophilic Xylanase

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

DNA Psi-condensation and reentrant decondensation: Effect of the PEG degree of polymerization

psi-Condensation of DNA fragments of about 4 kbp was induced by poly(ethylene glycol) (PEG), with degrees of polymerization ranging from 45 to 182, and univalent salt (NaCl). Using circular dichroism spectroscopy, we were able to accurately determine the critical amount of PEG needed to induce condensation, as a function of the NaCl concentration. A significant dependence on the PEG degree of polymerization was found. Phase boundaries determined for the multimolecular condensation were very similar to those observed previously for the monomolecular collapse, with two asymptotic regimes at low and high salt concentrations. We analyze our data using a theoretical model that properly takes into account both the polyelectrolyte nature of the DNA and the liquid crystallinity of the condensed phase. The model assumes that all PEG is excluded from the condensates and shows reentrant decondensation only at low salt. We also systematically study reentrant decondensation and find a very strong dependence on PEG molecular weight. At low PEG molecular weight, decondensation occurs at relatively low concentrations of PEG, and over a wide range of salt concentrations. This suggests that in the reentrant decondensation the flexible polymers used are not completely excluded from the condensed phase.

Measurement of the isolated photon cross section in p(p)over-bar collisions at root s=1.96 TeV

The cross section for the inclusive production of isolated photons has been measured in p (p) over bar collisions at root s = 1.96 TeV with the DO detector at the Fermilab Tevatron Collider. The photons span transverse momenta 23 to 300 GeV and have pseudorapidity vertical bar n vertical bar < 0.9. The cross section is compared with the results from two next-to-leading order perturbative QCD calculations. The theoretical predictions agree with the measurement within uncertainties. (c) 2006 Elsevier B.V. All rights reserved.

Gravitational and quantum bounds on the photon mass

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Search for large extra dimensions via single photon plus missing energy final states at root s=1.96 TeV

We report on a search for large extra dimensions in a data sample of approximately 1 fb(-1) of p (p) over bar collisions at root s=1.96 TeV. We investigate Kaluza-Klein graviton production with a photon and missing transverse energy in the final state. At the 95% C.L. we set limits on the fundamental mass scale M(D) from 884 to 778 GeV for two to eight extra dimensions.

Upper bounds on the photon mass

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Measurement of the differential cross section for isolated prompt photon production in pp collisions at 7 TeV

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Room temperature photoluminescence of BCT prepared by Complex Polymerization Method

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

High precision calculation of multipolar dynamic polarizabilities and two- and three-body dispersion coefficients of atomic hydrogen

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

New layered double hydroxides intercalated with substituted pyrroles. 1. In situ polymerization of 4-(1H-pyrrol-1-yl)benzoate

The two-dimensional hybrid organic-inorganic materials Zn-2-Cr and Zn-2-Al-LDHs (Layered Double Hydroxides) containing 4-(1H-pyrrol-1yl)benzoate anions as the interlayer anions were synthesized by the co-precipitation method at constant pH followed by subsequent hydrothermal treatment for 72 h. The materials were characterized by PXRD, C-13 CP-MAS NMR, ESR, TGA, and TEM. The basal spacing found by the X-ray diffraction technique is coincident with the formation of bilayers of the intercalated anions. Solid-state C-13 NMR and ESR data strongly suggest the partial in situ polymerization of the 4-(1H-pyrrol-1yl)benzoate anions during coprecipitation. (c) 2006 Elsevier Ltd. All rights reserved.