15 resultados para BIPYRIDINE COPOLYMERS

em Repositório Institucional UNESP - Universidade Estadual Paulista "Julio de Mesquita Filho"


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

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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The binding of the cations thallium(I), calcium(II) and terbium(III) to methyl methacrylate-methacrylic acid copolymers with different fractions of acid groups (x) has been studied in aqueous solution at, various pH values using the fluorescence of covalently bonded 9-vinyl anthracene as a probe. In all cases, the extent of binding increases as a function of the charge of the polymer with either increasing fraction of carboxylic acids or of pH. However, differences are observed in the behavior of the three cations, With Tl(I), quenching of the anthracene group fluorescence is observed. indicating that the thallium(I) approaches the probe and suggesting that the alkylanthracene is probably in a relatively polar region. Binding constants have been determined from anthracene quenching data and from studies with the fluorescent-probe sodium pyrenetetrasulfonate, Good agreement is obtained between the two methods, and values for the binding constants increase from 250 to 950 M-1 as x increases from 0.39 to 1. It is suggested that the cation is held in the polyelectrolyte domain, partly by Debye-Huckel effects and partly by more specific interactions. Stronger binding is found with calcium(II) and terbium(III), and in this case increases in fluorescence intensity are observed on complexation due to the anthracene group being in a more hydrophobic region, probably as a result of conformational changes in the polymer chain. In the former case the stoichiometry of the interaction was determined from the fluorescence data to involve two carboxylate groups bound per calcium. Association constants were found using murexide as an indicator of free calcium to vary from 8400 to 37 000 M-1 as x increases from 0.39 to 1. It is suggested that in this case specific calcium(II)-carboxylate interactions contribute to the binding. With terbium(III), a greater increase in the probe fluorescence intensity was observed than with calcium, and it is suggested that the interaction with the polymer is even stronger, leading to a more pronounced conformational change in the polymer. It is proposed that the terbium(III) interacts with sis carboxylic groups on the polymer chain, with three being coordinated and three attracted by electrostatic interactions.

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M(CO)(4)(N-N)] reacts with CuCl to give new heterobimetallic metal carbonyls of the type [M(CO)(4)(N-N)(CuCl)], M = W, Mo; N-N = 2,2'-bipyridine (bipy), 1,10-phenanthroline (phen). Reactions of [M(CO)(4)(N-N)(CuCl)] with NaSCN produced the series of complexes of general formula [M(CO)(4)(N-N)(CuSCN)]. The i.r. spectral of all the bimetallic carbonyls exhibited the general four m ( CO) band patterns of the precursors. The u.v.-vis. spectral data for precursors and products showed bands associated with pi --> pi* (nitrogen ligands), d-->d (intrametal), as well as MLCT d-->pi* (nitrogen ligands) and MLCT d --> pi*(CO) transitions. The [M(CO)(4)(N-N)(CuX)] (X = Cl, SCN) emission spectra showed only one band associated with the MLCT transition. The t.g. curves revealed a stepwise loss of CO groups. The initial decomposition temperatures of the [M(CO)(4)(N-N)(CuX)] series suggest that the bimetallic compounds are indeed thermally less stable than their precursors, and the X- ray data showed the formation of MO3, CuMO4, Cu2O and CuO as final decomposition products, M = W, Mo. The spectroscopic data suggests that the heterobimetallic compounds are polymeric.

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The temperature dependence has been investigated for the photoinduced birefringence in Langmuir-Blodgett (LB) films from the azocopolymer 4-[N- ethyl -N-(2-hydroxyethyl)] amino-2'-chloro-4'-nitroazobenzene (MMA-DR13) mixed with cadmium stearate. The buildup and relaxation of the birefringence in the range from 20 to 296 K were fitted with a Kohlrausch-Williams-Watts (KWW) function, with a beta-value of 0.78-0.98 for the build-up and 0.18-0.27 for the decay. This is consistent with a distribution of time constants for the kinetics of the birefringence processes. The maximum birefringence increased with increasing temperature up to 120 K because the free volume fluctuation also increased with temperature. Above 120 K, the birefringence decreased with temperature as thermal diffusion dominates. In the latter range of temperature, an Arrhenius behavior is inferred for both build-up and decay of birefringence. In each case two activation energies were obtained: 0.8 and 5 kJ/mol for the build-up and 10 and 30 kJ/mol for the decay. The energies for the build-up are much lower than those associated with motion of the polymer chain, which means that the dynamics is governed by the orientation of the chromophores. For the decay, local motion of lateral groups of the polymer chains becomes important as the activation energies are within the range of gamma-relaxation energies. (C) 2003 Elsevier B.V. B.V. All rights reserved.

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This paper is aimed at addressing the differences observed in film properties when poly(vinylidene fluoride-trifluorethylene) P(VDF-TrFE) films are fabricated using distinct methods. Samples were obtained either from casting a solution or by compression molding from a molten phase and characterized by differential scanning calorimetry (DSC). It is shown that the main differences between melt-solidified and cast films arise from the thermal treatment inherent in the former samples.

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The interaction between sodium dodecylsulfate (SDS) and acrylic acid (AA)-ethyl methacrylate (EMA) copolymers has been investigated using steady state fluorescence and conductimetric measurements to assess the effect of the polymer composition on the aggregation process. Micropolarity studies using the ratio between the emission intensities of the vibronic bands of pyrene (I-1/I-3) and the shift of the fluorescence emission of pyrene-3-carboxaldehyde show, that the interaction of SDS with AA-EMA copolymers occurs at surfactant concentrations smaller than that observed for the pure surfactant in water and depends on the copolymer composition. The increase of ethyl methacrylate in the copolymers lowers the critical aggregation concentration (CAC) due to the larger hydrophobic character of the polymer backbone. The formation of aggregates on the macromolecule is induced mainly, by hydrophobic interactions, but the process is also influenced by the ionic strength due to the counter-ions of the polyelectrolyte.

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The morphological, mechanical and rheological properties of nylon 6/acrylonitrile-butadiene-styrene blends compatibilized with MMA-MA [poly(methyl methacrylate-comaleic anhydride)] copolymers were studied. A twin screw extruder was used for melt-blended the polymers and the injection moulding process was used to mold the samples. The main focus was on nylon 6/ ABS blends compatibilized with one MMA-MA copolymer. This copolymer has PMMA segments that appear to be miscible with the styrene-acrylonitrile (SAN) phase of ABS and the anhydride groups can react with amine end groups of the nylon 6 (Ny6) to form graft copolymers at the interface between Ny6 and ABS rich phases. Tensile and impact and morphological properties were enhanced by the incorporation of this copolymer. Transmission electron microscopy (TEM) observations revealed that the ABS domains are finely dispersed in nylon 6 matrix and led to the lowest ductile-brittle transition temperatures and highest impact properties. It can be concluded that the MMA-MA copolymer is an efficient alternative for the reactive compatibilization and can be used as a compatibilizer for nylon 6/ABS blends.© 2003 Kluwer Academic Publishers.

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Nylon6 is an attractive polymer for engineering applications because it has reactive functionality through amine and carboxyl end groups that are capable of reacting. For this reason, it has been used a lot in polymeric blends. Blends of nylon6/ABS (acrylonitrile-butadiene-styrene) were produced using glycidyl methacrylate-methyl methacrylate (GMA-MMA) copolymers as compatibilizer. The binary blends were immiscible and exhibited poor mechanical properties that stemmed from the unfavorable interactions among their molecular segments. This produced an unstable coarse phase morphology and weak interfaces between the phases in the solid state. The presence of the copolymer in the blends clearly led to a more efficient dispersion of the ABS phase and consequently optimized Izod impact properties. However, the compatibilized blend showed poor toughness at room temperature and failed in a brittle manner at subambient temperatures. © 2005 Springer Science + Business Media, Inc.

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

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)