Evidences of phase separation in moisture‐cured poly(urethane urea)s by means of temperature modulated differential scanning calorimetry

The degree of phase separation in several moisture‐cured poly(urethane urea)s (PUUs) was studied by FTIR spectroscopy, wide angle X‐ray diffraction (WAXD), and temperature‐modulated differential scanning calorimetry (TMDSC). This latter technique was shown to be particularly useful in analysing the degree of phase separation in PUU polymers. Both phase mixing and phase segregation coexisted in the PUUs and the degree of phase separation increased as the urea hard segment (HS) content in the PUU increased. The maximum solubility of urea HSs into the polyol soft segments (SSs) was achieved for 50 wt % urea HS content in diol‐based PUUs, whereas for triol‐based PUUs the highest solubility between HS and SS was reached for lower urea HS amount. Finally, the higher the urea HS content the higher the extent of phase separation in the PUU. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3034–3045, 2007     

Novel acrylic macromonomer with amphiphilic character derived from Triton X‐100: Radical copolymerization with methyl methacrylate and thermal properties

This article explores the synthesis of a novel methacrylic macromonomer with an amphiphilic character derived from poly(ethylene glycol) tert‐octylphenyl ether (MT) and its respective homopolymer. To know their reactivity in radical copolymerization reactions with methyl methacrylate (MMA), a model monomer (MTm) was synthesized to determine the reactivity ratios and compare them with the low molar fractions of copolymers of MT with MMA because they were difficult to isolate. They were r_MTm = 0.97 and r_MMA = 0.95. The compositional diagrams when representing the weight fraction of MT and MTm in the feed and the copolymer suggested that a clear correlation exists between the experimental points of the model monomer MTm and the macromonomer MT ones, suggesting that the length of the side poly(ethylene oxide) chain does not affect the reactivity of the methacrylic double bond in the prepared monomers for this type of polymerization reaction. The reactivity ratios of the copolymers have a tendency for the formation of random or Bernoullian copolymers. The glass‐transition temperatures (T_g's) of the prepared copolymers were determined by differential scanning calorimetry, deviated from the Fox equation, and discussed on the basis of treatments that consider the influence of the monomeric units along the copolymer chains, determining the T_g of the corresponding alternating dyads. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1641–1649, 2003     

Diphenylmethane transformations over boron trifluoride modified alumina and silica-alumina

Transformations of diphenylmethane were investigated in a flow system in the presence of alumina and silica-alumina modified with boron trifluoride at atmospheric pressure and elevated temperatures. Hydrogen transfer reaction was observed on addition of tetralin to the substrate stream. This revised version was published online in August 2006 with corrections to the Cover Date.     

Preparation and properties of homogeneous V2O5-SiO2 xerogel composite based on interpenetrating polymer network

In this paper, we report the conducting and electrochemical properties of a homogeneous V₂O₅-SiO₂ xerogel composite obtained from the simultaneous polymerization in both inorganic components (Si-O and V-O based polymers) forming an interpenetrating polymer network, where a mutual “solubility” due to cross-links and entanglements was observed. The presence of V₂O₅ inside the silica matrix has a strong effect on electrical conductivity; measurements showed room temperature conductivity almost 1000 times higher than what is found in the literature. In addition, the electrochemical behavior is quite similar to that found in V₂O₅ xerogel. Moreover, the effects of thermal treatment on the conducting and electrochemical properties were investigated. It was found that both properties were improved with no significant effect on V₂O₅ xerogel layered structure.     

Hydrophilic and hydrophobic copolymer systems based on acrylic derivatives of pyrrolidone and pyrrolidine

This article deals with the synthesis of hydrophilic methacrylic monomers derived from ethyl pyrrolidone [2‐ethyl‐(2‐pyrrolidone) methacrylate (EPM)] and ethyl pyrrolidine [2‐ethyl‐(2‐pyrrolidine) methacrylate (EPyM)] and their respective homopolymers. For the determination of their reactivity in radical copolymerization reactions, both monomers were copolymerized with methyl methacrylate (MMA), the reactivity ratios being calculated by the application of linear and nonlinear mathematical methods. EPM and MMA had ratios of r_EPM = 1.11 and r_MMA = 0.76, and this indicated that EPM with MMA had a higher reactivity in radical copolymerization processes than vinyl pyrrolidone (VP; r_VP = 0.005 and r_MMA = 4.7). EPyM and MMA had reactivity ratios of r_EPyM = 1.31 and r_MMA = 0.92, and this implied, as for the EPM–MMA copolymers, a tendency to form random or Bernoullian copolymers. The glass‐transition temperatures of the prepared copolymers were determined by differential scanning calorimetry (DSC) and were found to adjust to the Fox equation. Total‐conversion copolymers were prepared, and their behavior in aqueous media was found to be dependent on the copolymer composition. The swelling kinetics of the copolymers followed water transport mechanism case II, which is the most desirable kinetic behavior for a swelling controlled‐release material. Finally, the different states of water in the hydrogels—nonfreezing water, freezing bound water, and unbound freezing water—were determined by DSC and found to be dependent on the hydrophilic and hydrophobic units of the copolymers. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 395–407, 2003     

UPML formulation for truncating conductive media in curvilinear coordinates

This work presents a formulation based on UPML for truncating conductive media by using a local and non-orthogonal coordinate system to solve Maxwell’s equations by the FDTD method. The detailed procedure for obtaining the UPML equations for this case is shown and the complete equation set is provided.     

The prediction of coal properties using compressed infrared data from osculating polynomials

Reduction of the representation of infrared spectra from coal samples by osculating polynomials of degree nine is discussed. The reduced representation contains polynomial coefficients of order zero to four. Mathematical models of the original spectra are obtained by linear combination of the coefficients. These compressed models are statistically correlated to coal properties, namely, volatile matter, fixed carbon, ash content, heating value, hydrogen, carbon, sulphur, nitrogen, and maximum vitrinite reflectance, and the results are compared with those previously obtained from second derivatives of the same spectra. The use of compressed data, while giving slightly better correlations for some of the properties, has the advantage of requiring less computational time.     

Boundary G/G Theory and Topological Poisson–Lie Sigma Model

We study a boundary version of the gauged WZW model with a Poisson–Lie group G as the target. The Poisson–Lie structure of G is used to define the Wess–Zumino term of the action on surfaces with boundary. We clarify the relation of the model to the topological Poisson sigma model with the dual Poisson–Lie group G ^* as the target and show that the phase space of the theory on a strip is essentially the Heisenberg double of G introduced by Semenov–Tian–Shansky.