Alargamento da distribuição de massa molar de polímeros sintetizados com catalisadores metalocênicos dual-site

The main topics related to the use of dual-site catalysts in the production of polymers with broad molecular weight distribution are reviewed. The polymerization using dual-site catalysts is more economical and allows to produce a higher quality product than other processes, such as polymer blend and multistage reactors. However, the formulation of these catalysts is quite complicated since the same catalyst must produce distinct polymer grades. In addition, the release of patents concerning the combination of metallocenes and new technologies for polymerization shows that polymerization processes using dual-site catalysts are of current industrial interest.

A química supramolecular de complexos pirazólicos

The purpose of this review is to describe the progress in the supramolecular chemistry of the pyrazolyl-based metal complexes. The text is written under the structural point of view, emphasizing the role of the covalent and non-covalent interactions in the rational construction of super and supramolecules.

Um estudo teórico de propriedades moleculares em complexos de hidrogênio trimoleculares C2H4···2HF, C2H2···2HF e C3h6···2HF

We present a theoretical study of molecular properties in C2H4···2HF, C2H2···2HF and C3H6···2HF trimolecular hydrogen-bonded complexes. From B3LYP/6-311++G(d,p) calculations, the most important structural deformations are related to the C=C (C2H4), C≡C (C2H2), C-C (C3H6) and HF bond lengths. According to the Bader's atoms in molecules and CHELPG calculations, it was identified a tertiary interaction between the fluorine atom of the second hydrofluoric acid molecule and hydrogen atoms of the ethylene and acetylene within the C2H4···2HF and C2H2···2HF complexes, respectively. Additionally, the evaluation of the infrared spectrum characterized the new vibrational modes and bathochromic effect of the HF molecules.

Argilas como catalisadores verdes na esterificação do colesterol: caracterização espectroscópica e identificação de polimorfos por métodos de análise térmica. Uma proposta laboratorial interdisciplinar para o 1º ciclo universitário

A laboratory experiment that enables the professor to introduce the problematic of sustainable development in pharmaceutical chemistry to undergraduate students is proposed, using a simple synthetic procedure. Cholesteryl acetate is prepared by the esterification of cholesterol using Montmorillonite K10 as heterogeneous catalyst. Cholesterol and cholesteryl acetate are characterized by spectroscopic (¹H RMN, 13C RMN, FTIR) and thermal analysis techniques. The thermal methods are used to introduce the concepts of polymorphism and the nature of mesophases.

Síntese e caracterização de complexos de platina(IV) com derivados N-benzilados da 1,3-propanodiamina

The present work describes the synthesis of a series of platinum(IV) complexes with N-benzyl 1,3-propanediamine derivatives. Since substitution of the axial ligands in the platinum(IV) complexes may alter their pharmacological properties, we have prepared complexes with different groups, such as hydroxide, chloride and acetate using a sequence of substitution reactions. The resulting complexes were fully characterized by IR, ¹H, 13C and 195Pt NMR spectroscopies, and elemental analysis.

Análise por componentes principais de espectros nexafs na especiação do molibdênio em catalisadores de hidrotratamento

Bulk and supported molybdenum based catalysts, modified by nickel, phosphorous or tungsten were studied by NEXAFS spectroscopy at the Mo L III and L II edges. The techniques of principal component analysis (PCA) together with a linear combination analysis (LCA) allowed the detection and quantification of molybdenum atoms in two different coordination states in the oxide form of the catalysts, namely tetrahedral and octahedral coordination.

Preparação e caracterização espectroscópica de complexos de boro: uma proposta para uma prática integrada de química inorgânica

As a proposal for an undergraduate second or third year inorganic laboratory course, the present paper describes the preparation of three representative boron complexes: potassium tetrafluoroborate, pyridoxin boron complex and potassium bis(oxalato)borate. The complexes are characterised by infrared and multinuclear magnetic resonance spectroscopy (¹H, 11B and 19F) where isotopic effects are demonstrated.

Catalisadores heterogêneos para a produção de monoésteres graxos (biodiesel)

The recent increase in the world biodiesel demand, along with the need to reduce costs while improving the environmental sustainability of the entire biodiesel production chain, have led to the search for heterogeneous catalysts that would be efficient and highly amenable to recycling. Many classes of materials have been tested for these purposes. Among these are zeolites, ion-exchange resins, inorganic oxides, guanidines, metal complexes, layered compounds and ionic liquids. This review article describes the structure, properties, synthesis and performance of compounds that are catalytic active in both esterification and transesterification reactions.

Catalisadores metalocênicos suportados para a produção de poliolefinas: revisão das estratégias de imobilização

The inadequacy of strategies used for the heterogeneization of metallocene catalysts is pointed out as one of the main causes of the lack of industrial employability of such polymerization catalysts. The main problems are the necessity of large quantity of MAO (cocatalyst) and the inability to control molecular mass distribution of the polymers. Based on this background, the main strategies for the heterogeneization of metallocenes are here reviewed. The advantages and disadvantages of each strategy are presented and discussed on theoretical and practical perspective. Considering the results reported on the different researches, outcomes of heterogeneization strategies are pointed out.

Co2 na desidrogenação oxidativa do etilbenzeno utilizando catalisadores compostos de óxido de ferro e óxido de alumínio

Materials containing aluminum and iron oxide were synthesized through the preparation of hybrid spheres and tested in the dehydrogenation of ethylbenzene in the presence of CO2. The catalytic results suggest that the high initial ethylbenzene conversion is due to the contribution of basic sites. These results also point to a competitive process between CO2 adsorption and the oxidative dehydrogenation of ethylbenzene for the basic sites (lattice oxygen). In spite of the coke deposition is originating from ethylbenzene and CO2, the amount of carbonaceous deposits was smaller with the presence of CO2, if compared with the dehydrogenation in the absence of CO2.

Esterificação de ácidos graxos utilizando zircônia sulfatada e compósitos carvão ativado/zircônia sulfatada como catalisadores

In this work sulfated zirconia (SZr) and activated carbon/SZr composites produced by impregnation method with or without heating treatment step (CABC/SZr-I and CABC/SZr-I SC) and by the method of synthesis of SZr on the carbon (CABC/SZr-S) was used as catalysts in the esterification reactions of fatty acids. The SZr presented very active, conversions higher than 90% were obtained after 2 h of reaction. The activity of the composite CABC/SZr-I20%SC was up to 92%, however, this was directly related to time and temperature reactions. CABC/SZr-I and CABC/SZr-S were less active in esterification reactions, what could be attributed to its low acidity

Emprego de catalisadores heterogêneos de CaO e SnO2 suportados em cinza de casca de arroz na obtenção de biodiesel

Silica obtained from rice husk after acid leaching and calcination was compared to commercial silica as a catalyst support. CaO and SnO2 catalysts were prepared by impregnation and tested in the transesterification of soybean oil and the esterification of oleic acid. CaO catalysts showed basic character and were the most active for transesterification, whereas SnO2 catalysts were acid and the most effective for esterification. In both cases the performances of the catalysts prepared with rice husk ash and commercial silica were similar. These results demonstrate that rice husk is a cost-effective and environmentally-friendly source of silica that can be used as a catalyst support.

O efeito da desativação térmica nas propriedades oxirredutoras e na atividade catalítica de catalisadores CZ e Pd-CZ

Automotive catalyst, using in Brazil since 1992, is a essential technology for vehicular emissions control. Noble metals are the active phase of these catalysts, and cerium zirconium mixed oxides (CZ), responsibles for the oxygen storage capacity (OSC), one of the most important aspect for the operational performance of the catalyst. In this context, the oxireduction properties analysis of CZ and Pd/CZ (palladium supported in CZ) system are the objective of this study, as well as, the impact of the thermal aging in the OSC. Aging consisted of treatments at 900 or 1200 °C, for 12 or 36 h, in oxidizing condition.

Efeito da adição de lantânio em catalisadores de Ni/ZrO2 aplicados na reação de reforma a vapor de etanol

The catalytic performance of Ni/ZrO2 catalysts loaded with different lanthanum content for steam reforming of ethanol was investigated. Catalysts were characterized by BET surface area, X-ray diffraction, UV-vis spectroscopy, temperature programmed reduction, and X-ray absorption fine structure techniques. Results showed that lanthanum addition led to an increase in the degree of reduction of both NiO and nickel surface species interacting with the support, due to the higher dispersion effect. The best catalytic performance at 450 ºC was found for the Ni/12LZ catalyst, which exhibited an effluent gaseous mixture with the highest H2 yield.

Hidrólise de celulose por catalisadores mesoestruturados NiO-MCM-41 e MoO3-MCM-41

This study was carried out to synthesize, characterize and evaluate the application of mesoestruturated catalysts MCM-41, 5%MoO3-MCM-41 and 5%NiO-MCM-41 in the hydrolysis of microcrystalline cellulose. XRD results indicate that the phase of mesoporous MCM-41 was obtained and that the introduction of metal oxides did not affect this mesoporous phase. About the heterogeneous hydrolysis reaction, it was observed that the increase in temperature results in a higher concentration of glucose and the catalyst 5%MoO3-MCM-41 provides the highest concentrations of glucose.