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     

Glass transitions and mixed phases in block SBS

Differential scanning calorimetry (DSC) does not allow for easy determination of the glass‐transition temperature (T_g) of the polystyrene (PS) block in styrene–butadiene–styrene (SBS) block copolymers. Modulated DSC (MDSC), which deconvolutes the standard DSC signal into reversing and nonreversing signals, was used to determine the (T_g) of both the polybutadiene (PB) and PS blocks in SBS. The T_g of the PB block was sharp, at ?92 °C, but that for the PS blocks was extremely broad, from ?60 to 125 °C with a maximum at 68 °C because of blending with PB. PS blocks were found only to exist in a mixed PS–PB phase. This concurred with the results from dynamic mechanical analysis. Annealing did not allow for a segregation of the PS blocks into a pure phase, but allowed for the segregation of the mixed phase into two mixed phases, one that was PB‐rich and the other that was PS‐rich. It is concluded that three phases coexist in SBS: PB, PB‐rich, and PS‐rich phases. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 276–279, 2005     

Carboxylic fused furans for amino acid fluorescent labelling

Four carboxylic fused furans are presented as new fluorescent labels for the amino and hydroxyl functions of organic molecules. Various representative l-amino acids were chosen as models, labelled at their N-terminus and also at their side-chain. Fluorescent derivatives were obtained in high yields, and their absorption and emission properties were studied.     

Ab initio modelling of crosslinking in polymers. A case of chains with furan rings

A quantum chemical model (Abinitio HF-MO and DFT-B3LYP) of polyfurfuryl alcohol crosslinking is shown. Two pathways were considered: (a) a Diels–Alder (D–A) reaction between a dihydrofuran moiety and a furan ring; (b) the addition reaction of electrophilic specimens on conjugated double bonds. The ability for the formation of D–A adducts (dienes and dienophiles) was investigated by the frontier molecular orbital (FMO) theory. Energy gaps between the FMO's of diene and dienophile structures suggest that the occurrence of the D–A reaction is possible. The results suggest that the carbons of the exo double bonds attached to dihydrofuran rings are the sites most likely to be attacked by electrophilic species, while the C₃ and C₄ atoms display the opposite tendency due to their low HOMO electron densities. Results of a thermochemical approach to these reactions at the MP2 level was in agreement with reactivity modelled by MO predictions.     

Bending loss measurement using a fiber cavity ringdown scheme

A novel sensitive technique for the determination of losses in fiber cavities is presented. The method is based on the cavity ringdown scheme implemented in silica-based single-mode fibers. Bending losses of fiber cavities of different lengths have been measured showing all an oscillating behavior with respect to the curvature radius of the fiber as predicted by a theoretical model. The best minimum detectable absorbance per cavity pass achieved by this new method is 1.72×10⁻³ dB within a 10 m-long cavity. This limit suffices well for an accurate determination of optical bending losses even in bend-insensitive fibers. Furthermore, the comparison of the measured bending losses with a theoretical model allows the extraction of different fiber parameters. Good agreement has been found between the experimentally derived parameters and literature data.     

Lightly crosslinked,mesomorphic networks obtained through the reaction of dimeric,liquid‐crystalline epoxy–imine monomers and heptanedioic acid

We reacted various dimeric, liquid‐crystalline epoxy–imine monomers, differing in the length of the central aliphatic spacer or the dipolar moments, with heptanedioic acid. The resulting systems showed a liquid‐crystalline phase in some cases, depending on the dimer and on the reaction conditions. The systems were characterized with respect to their mesomorphic properties and then were submitted to dynamic mechanical thermal analysis in both fixed‐frequency and frequency‐sweep modes in the shear sandwich configuration. The arrangement in the liquid‐crystalline phase seemed to be mainly affected both by the polarization of the mesogen and by the reaction temperature, which favored the liquid‐crystalline arrangement when it was lying in the range of stability of the dimer mesophase. In agreement with other recent literature data, dynamic mechanical thermal analysis results suggested that the presence of the mesogen directly incorporated into the main chain increased the lifetimes of the elastic modes both in the isotropic phase and in the liquid‐crystalline phase with respect to side‐chain liquid‐crystalline elastomers and that the time–temperature superposition principle did not hold through the liquid‐crystalline‐to‐isotropic transition. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44:6270–6286, 2006     

Vinyl‐terminated side‐chain liquid‐crystalline polyethers containing mesogenic benzylideneaniline moieties

The synthesis of two vinyl‐terminated side‐chain liquid‐crystalline polyethers containing benzylideneaniline moieties as mesogenic cores was approached in two different ways: by chemically modifying poly(epichlorohydrin) with suitable mesogenic acids or by polymerizing analogous glycidyl ester or glycidyl ether derivatives. In all the conditions tested, the first approach led to materials in which the imine group was hydrolyzed. The second approach led to the desired polymers PG2a and PG2b , but only from the glycidyl ether derivatives and when the initiator was the system that combined polyiminophosphazene base t‐Bu‐P₄ and 3,5‐di‐t‐butylphenol. These polymers were chemically characterized by IR and ¹H and ¹³C NMR spectroscopies. The estimated degrees of polymerization ranged from 30 to 36. The liquid crystalline behavior of the synthesized polymers was studied by differential scanning calorimetry, polarized optical microscopy (POM) and X‐ray diffraction. Both polymers behave like liquid crystals and exhibited a single mesophase, which was recognized as a smectic C mesophase, probably with a bilayer arrangement, i.e., a smectic C₂ mesophase. The crosslinking of both polymers was performed with dicumyl peroxide as initiator, which led to liquid crystalline thermosets. POM and X‐ray diffraction confirmed that the mesophase organization mantained on the crosslinked materials. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1877–1889, 2006