Polymerization of diethyl vinylphosphonate (DEVP) is achieved by using lanthanide tris(borohydride) complexes, Ln(BH₄)₃(THF)₃ (Ln = Y, La, Nd, Sm, Gd, Dy, Lu) as an initiator. The characteristics and mechanism of polymerization as well as the properties of the resulting poly(diethyl vinylphophonate)s (PDEVPs) are studied. The effects of the lanthanide elements, the molar ratios of monomer to initiator ([M]/[ln]), reaction temperature and time on polymerization have been investigated in detail. The optimized polymerization conditions are 40 °C, 1 h in bulk with [M]/[ln] = 300. The kinetic study indicates that the polymerization of DEVP undergoes a controlled manner as the molecular weights (MWs) of PDEVPs increase with monomer conversion linearly maintaining moderate MW distribution (1.7–1.9). Additionally, a coordination anionic polymerization mechanism is proved by end-group analysis with ESI mass and ¹H NMR spectroscopy. The obtained PDEVPs have low glass transition temperature (T_g = −62 °C) and high thermal decomposition temperature (T_d > 300 °C) determined by differential scanning calorimetry and thermogravimetric analysis respectively. The thermosensitive behavior of PDEVP is characterized by evaluating the lower critical solution temperature of PDEVP in water by ultraviolet transmittance. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2409–2415

Main-chain imidazolium-functionalized amphiphilic block copolymers (PIL-b-PS) consisting of polyionic liquid (PIL) and polystyrene (PS) blocks have been first synthesized by condensation polymerization combined with nitroxide-mediated free radical polymerization (NMP). The di-functional imidazolium-based ionic liquid (IL) having both hydroxyl and ester end groups was synthesized through Michael addition between imidazole and methylacrylate (MA) and further quaternization by 2-chloroethanol. The HTEMPO (4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy) terminated polyionic liquid (HTEMPO-PIL) as the hydrophilic block was prepared by condensation polymerization of di-functional imidazolium IL and HTEMPO at a certain ratio. The hydrophobic PS block was synthesized by controlled radical polymerization of styrene using HTEMPO-PIL through NMP, resulting PIL-b-PS block copolymers. The structure of block copolymers obtained has been characterized and verified by FTIR, ¹H NMR, and size exclusion chromatography analyses. In addition, the morphology and size of the micelles formed by PIL-b-PS block copolymers in water were investigated by transmission electron microscopy and dynamic light scattering. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

A series of positively charged imidazolium-functionalized ionic polyurethanes (IPUs) were prepared in one-step polymerization process by polymerization of presynthesized short-chain imidazolium-based ionic diol, polyethylene glycols with different molecular weights as long-chain diols, and toluylene-2,4-diisocyanate. The structures of IPUs are confirmed by ¹H NMR analysis, and the thermogravimetric analysis measurement indicates that the IPUs have high degradation temperature. Fluorescent nanocrystal–polymer composites CdTe–IPU can be prepared conveniently, by the electrostatic interaction between positively charged IPUs and the negatively charged aqueous CdTe quantum dots (QDs). UV–vis absorption and photoluminescence spectra indicate the photochemical stability and strong fluorescent emission of CdTe–IPU composites. The quantum yields (QYs) of the composites are high and basically restore the QYs of the pure QDs. In addition, the transmission electron microscopy photographs show that the QDs in composites are uniform (about 3 nm in diameter) and monodisperse. The obtained nanocomposites are powder or elastomers with good film building. The casted CdTe–IPU films are transparent under visible light, and the colors of the composites and their films are vivid under a UV lamp. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

A series of yttrium trisalicylaldimine complexes formed in situ by the reaction of trialkyl complex [Y(CH₂SiMe₃)₃(THF)₂] (THF is tetrahydrofuran) with three equivalent salicylaldimines were used as initiators for the ring-opening polymerization of ε-caprolactone. Electronic and steric effects of the salicylaldimine ligand played important roles on the catalytic properties of the yttrium complexes. The yttrium trisalicylaldimine complex Y(L7)₃ (L7 = (S)-2,4-di-tert-butyl-6-[(1-phenylethylimino)methyl]phenol) most effectively initiated controlled ring-opening polymerization of ε-caprolactone to prepare poly(ε-caprolactone)s with high molecular weights and moderate molecular weight distributions. Obtained by density functional theory calculations, the optimized geometries of the four different active centers with four salicylaldimine ligands explained the experimental results. Copyright © 2011 Society of Chemical Industry

Amphiphilic hyperbranched poly(amino ester)s with hydrophilic multi-ethoxylated triacrylate backbone and hydrophobic long alkyl side chain were firstly synthesized via one pot Michael addition polymerization. The poly-(amino ester) could dissolve in cold water and self-assemble into loose micelle. Under 50–1000 ms bubble, the dynamic surface tension (DST) of the poly(amino ester) aqueous solution (0.5 wt%) still maintained in the range of 32–28 mN/m. The aqueous solutions of poly(amino ester)s with different molecular weights showed the lower critical solution temperature (LCST) in the range of 8–50°C, which could also be tuned by its pH. Capped with hydrophobic groups on the terminal units and partially neutralized with acid, the poly(amino ester)s still kept their stable dynamic surfactant behaviors, indicating promising application.