Chelate polymers: II. Some novel transition metals complexes with azomethine‐containing siloxanes and their polyesters

New Schiff bases of 2,4‐dihydroxybenzaldehyde with siloxane‐α,ω‐diamines having different numbers of siloxane units in the chain have been synthesized and characterized by spectroscopy, elemental and thermal analyses. These azomethines were found to form complexes readily with copper(II), nickel(II), cobalt(II), cadmium(II) and zinc(II). From IR and UV–Vis studies, the phenolic oxygen and imine nitrogen of the ligand were found to be the coordination sites. Thermogravimetric analysis (TGA) data indicate the chelates to be more stable than the corresponding ligands. The melting points increase with shortening of the siloxane segment from azomethine, as well as the result of complexation. The chelates obtained were covalently inserted in polymeric linear structures by polycondensation through the OH‐difunctionalized ligand with 1,3‐bis(carboxypropyl)tetramethyldisiloxane. Direct polycondensation, assisted either by acetic anhydride or N,N′‐dicyclohexylcarbodiimide as dehydrating agent and the complex 4‐(dimethylamino)pyridinium 4‐toluenesulfonate as catalyst, was used for the synthesis of these compound types. The structures of the polymers obtained were confirmed by IR, UV and ¹H NMR. Characterization was undertaken by TGA, solubility tests and viscosity measurements. Copyright © 2003 John Wiley & Sons, Ltd.     

Influence of heat treatment conditions on the porosity changes of sulfonated styrene/divinylbenzene copolymers

Sulfonic cation exchangers with two ion exchange group concentrations (0.5 and 2.4 mmol/g, samples A and B, respectively) were obtained by sulfonation of a porous styrene (S) and divinylbenzene (DVB) copolymer with chlorosulfonic acid. Strong thermal decomposition of the sulfonated copolymer A, accompanied by significant changes in its porous structure, starts at ca. 400°C. The char has no sulfonic groups. After heat treatment at 400°C in steam, a sorbent was obtained (yield 65%) that shows higher phenol sorption than the untreated sample when related to the bed volume. The chlorosulfonic derivatives of the initial copolymer were less thermally resistant than the sulfonic ones obtained by hydrolysis. Pyrolysis of the cation exchanger B, in its H+ and Ca²⁺ forms, was carried out at 900°C (yield of both chars close to 30%). By subsequent steam activation at 800°C to a 50% burn-off of the char, sorbents with well-developed, but distinctly different, porous structures were obtained. The activated char from the sulfonated copolymer in its hydrogen form was highly microporous and indicated an effective surface area of 1180 m²/g. However, because of a low contribution of mesopores, its ability to adsorb phenol from the liquid phase was not very high. The activated char from the calcium-doped copolymer, indicating a smaller surface area (580 m²/g) but characterized by a well-developed mesoporosity, was a better sorbent for phenol. © 1994 John Wiley & Sons, Inc.     

An analytical proof of Hardy-like inequalities related to the Dirac operator

We prove some sharp Hardy-type inequalities related to the Dirac operator by elementary, direct methods. Some of these inequalities have been obtained previously using spectral information about the Dirac-Coulomb operator. Our results are stated under optimal conditions on the asymptotics of the potentials near zero and near infinity.     

Nanostructured polymetallaynes of controlled length: Synthesis and characterization of oligomers and polymers from 1,1′‐bis‐(ethynyl)4,4′‐biphenyl bridging Pt(II) or Pd(II) centers

The reactivity of square planar palladium(II) and platinum(II) complexes in trans or cis configuration, namely trans or cis‐[dichlorobis(tributylphosphine)platinum(II)] and trans‐[dichlorobis(tributylphosphine)palladium(II)] with 1,1′‐bis(ethynyl) 4,4′‐biphenyl, DEBP, leading to π‐conjugated organometallic oligomeric and polymeric metallaynes, was investigated by a systematic variation of the reaction conditions. The formation of polymers and oligomers with defined chain length [? M(PBu₃)₂ (C?C? C₆H₄? C₆H₄? C?C? )]_n (n = 3–10 for the oligomers, n = 20–50 for the polymers) depends on the configuration of the precursor Pt(II) and Pd(II) complexes, the presence/absence of the catalyst CuI, and the reaction time. A series of model reactions monitored by XPS, GPC, and NMR ³¹P spectroscopy showed the route to modulate the chain growth. As expected, the nature of the transition metal (Pt or Pd) and the molecular weight of the polymers markedly influence the photophysical characteristics of the polymetallaynes, such as optical absorption and emission behavior. Polymetallaynes with nanostructured morphology could be obtained by a simple casting procedure of polymer solutions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3311–3329, 2007     

Cetyltrimethylammonium hydroxide (CTAOH) as a general, ecofriendly catalyst for the formation of carbon-carbon bond through nitroalkanes

Nitroalkanes have been found to give good yields in Michael and nitroaldol (Henry) reactions by the use of a catalytic amount (10 mol%) of CTAOH, at room temperature and under solvent free conditions and in very short reaction times. The methods do not need a large excess of the nitroalkanes and show good chemoselectivity toward further functionalities.     

Pressure-temperature phase diagrams of smectogenic 4'-alkyl-4-cyanobiphenyls (9CB, 10CB, 11CB and 12CB)

The pressure-temperature ( p - T ) phase diagrams for four smectogenic members of the 4'-alkyl-4-cyanobiphenyl homologous series ( n CB, n =9, 10, 11 and 12) over the temperature range 320-410 K and pressure range 0.1-300 MPa (3 kbar) were constructed using DTA. At 1 atm 9CB exhibits nematic and smectic A d phases, while the other members show only the smectic A d phase. However, at elevated pressures the clearing line splits in the case of 10CB and 11CB which indicates the induction of a nematic phase. It was found that the triple point, where the isotropic, nematic and smectic phases coexist, is strongly shifted to higher pressures with increasing chain length. This was interpreted as being caused by a loss of the rod-like shape of the molecules containing longer alkyl tails which explore a range of conformations. The slope of the clearing line, d T /d p , depends strongly on the length of the alkyl chain for the n CB series, but does not show a step-wise change between the nematogenic and smectogenic members.     

Bounds for non‐periodic mixtures of infinitely many materials

We prove bounds on the homogenized coefficients for general non‐periodic mixtures of an arbitrary number of isotropic materials, in the heat conduction framework. The component materials and their proportions are given through the Young measure associated to the sequence of coefficient functions. Upper and lower bounds inequalities are deduced in terms of algebraic relations between this Young measure and the eigenvalues of the H‐limit matrix. The proofs employ arguments of compensated compactness and fine properties of Young measures. When restricted to the periodic case, we recover known bounds. Copyright © 2005 John Wiley & Sons, Ltd.     

Effects of alcohols on micellization and on the reaction methyl 4‐nitrobenzenesulfonate + Br− in cetyltrimethylammonium bromide aqueous micellar solutions

The effects of n‐hexanol, n‐pentanol, and n‐butanol on the critical micelle concentration (cmc), on the micellar ionization degree (α), and on the rate of the reaction methyl 4‐nitrobenzenesulfonate + Br^? have been investigated in cetyltrimethylammonium bromide (CTAB) aqueous solutions. An increase in the alcohol concentration present in the solution produces a decrease in the cmc and an increase in the micellar ionization degree. Kinetic data show that the observed rate constant decreases as alcohol concentration increases. This result was rationalized by considering variations in the equilibrium binding constant of the methyl 4‐nitrobenzenesulfonate molecules to the micelles, variations in the interfacial bromide ion concentration, and variations in the characteristics of the water–alcohol bulk phase provoked by the presence of alcohols. When these operative factors are considered, kinetic data in this and other works show that the second‐order rate constants in the micellar pseudophases of water–alcohol micellar solutions are quite similar to those estimated in the absence of alcohols. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 634–641, 2004     

Cellulose-polyamide 66 blends. Part II: Mechanical behavior

Blends of the natural polymer cellulose with a synthetic polymer, polyamide 66, are studied in order to determine if the expected strong interaction between them, due to hydrogen bonds, could improve their mechanical properties such as strength and elongation at break. In a previous work {Part I, J. Polym. Sci. Polym. Phys., 32 , 1437 (1994)}, the preparation technique and the characterization of cellulose-polyamide 66 (PA66) blends were described in detail. Several samples in the composition range between 0 to 70 wt % of PA66 were carefully dried and examined using dynamic mechanical and tensile tests. Based on previous work a new percolation model has been developed. It takes both linear and nonlinear mechanical behaviors into account and allows for the effect of adhesion between material domains. From comparison between experimental and predicted data, it is concluded that a partial miscibility between the amorphous phases of cellulose and PA66 exists and is responsible for a strong adhesion at their interface. Solid-state ¹³C nuclear magnetic resonance has also been used to study these samples and supports the existence of strong interactions between both homopolymers. © 1995 John Wiley & Sons, Inc.