A facile and rapid preparation of 3-(2-aminoethylamino)propylheptaphenylPOSS (AA-POSS), a special phenyl-POSS that contains two functional amino groups (Scheme 1), is demonstrated by the corner-capping method. Then AA-POSS forms a series of novel phenyl-POSS/PU aqueous dispersions. The structure of AA-POSS has been confirmed by ¹H, ¹³C, ²⁹Si NMR, and ESI-MS. The POSS/PU hybrid films are studied by Fourier transform infrared spectrometer (FT-IR), gel permeation chromatography (GPC), scanning electron microscope (SEM), X-ray diffraction (XRD) spectra, differential scanning calorimetry (DSC) analysis, and thermal gravimetric analyzer (TGA). FT-IR and GPC are conducted to validate the chemical structure of the hybrid PU. The properties of hybrid films display significant changes with notable increases in T_g, thermal properties, tensile strength, as well as surface hydrophobicity. These changes are attributed to the incorporation of novel POSS into PU. Moreover, these significant material property enhancements are achieved at low levels of POSS incorporation (only 4%). © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1611–1620, 2013

An efficient direct method for di-, tri- and tetraformylation of thiacalix[4]arenes substituted on the para positions is described. Di- and triformylated thiacalix[4]arenes were obtained by formylation of partially propyl- or benzoyl-substituted thiacalix[4]arenes. Complete para-formylation was successfully achieved by formylation and dealkylation of tetraisopropoxythiacalix[4]arene conformers in one step. This experimental procedure is a simpler synthesis for completely formylated thiacalix[4]arene than the indirect method reported previously from brominated thiacalix[4]arene.

Novel aqueous polyurethane (PU) hybrid dispersions were successfully prepared with 5–15 mol % functionalized hexamethylene diisocynate trimer modified by N-(n-butyl)-3-aminopropyltriethoxysilane and dihydroxylpropyl-terminated siloxane oligomers (TS). The results of the differential scanning calorimetry and X-ray diffraction tests show that the degree of segment order was reduced by the introduction of TS. The hybrid polymer films with TS introduced into the PU backbone displayed excellent water and xylene resistance. Atomic force microscopy showed that the films had a smooth surface. It was noticeable that the tensile strength (σ_b) and Young's modulus of the films increased simultaneously when TS was incorporated into PU; σ_b of the PU15 film with 15 mol % TS was much higher than that of the neat PU0 film, and the breaking elongation of the film with 10 mol % TS was clearly higher than that of the other films. The results indicate that an appropriate content of TS significantly improved the properties of the aqueous PU hybrids. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

A novel Ag⁺ ionophore, p-tert-butyl-tetrakis(hydrazinocarbonylmethoxy)thiacalix[4]arene in 1,3-alternate conformation (thiacalix[4]arene tetrahydrazide, 1) was synthesized. Its binding properties towards alkali and transition metal cations were studied by noncompetitive liquid-liquid extraction of alkali metal (Li⁺, Na⁺, K⁺ and Cs⁺) and transition metal (Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Ag⁺) picrates. It was found that the thiacalix[4]arene tetrahydrazide exhibited high extractability towards Ag⁺, lower percent extraction towards Cu²⁺, and little or no extraction ability towards the others. The selectivity towards Ag⁺ was further evaluated by competitive Ag⁺ extraction experiments in the mixture of the above-mentioned nine cations, the concentration of which was monitored with ICP-OES. ¹H NMR titration experiments and ESI-MS proved the stoichiometry of 1 to Ag⁺ was 1:1, and the ′N-Ag⁺′ interaction with the assistance of thiacalixarene skeleton was primarily involved in the complexation.