Perovskite nanoparticles: Preparation by reactive milling and magnetic characteristics

La_0.7Sr_0.3MnO₃ and La_0.7Ca_0.3MnO₃ nanoparticles were synthesized by reactive milling method. Grain size determined from XRD, TEM, and magnetization measurements show an average diameter ?18 nm and decreasing with increasing milling time. DC and AC magnetic measurements evidenced an interacting superparamagnetism due to clustering of perovskite nanoferromagnets with spin dynamic time in range of 10⁻⁹–10⁻¹⁰ s.     

Living free‐radical polymerization of sterically hindered monomers: Improving the understanding of 1,1‐disubstituted monomer systems

The sterically hindered, 1,1‐disubstituted monomers di‐n‐butyl itaconate (DBI), dicyclohexyl itaconate (DCHI), and dimethyl itaconate (DMI) were polymerized with reversible addition–fragmentation chain transfer (RAFT) free‐radical polymerization and atom transfer radical polymerization (ATRP). Cumyl dithiobenzoate, cumyl phenyl dithioacetate, 2‐cyanoprop‐2‐yl dithiobenzoate, 4‐cyanopentanoic acid dithiobenzoate, and S‐methoxycarbonylphenylmethyl dithiobenzoate were employed as RAFT agents to mediate a series of polymerizations at 60 °C yielding polymers ranging in their number‐average molecular weight from 4500 to 60,000 g mol^?1. The RAFT polymerizations of these hindered monomers displayed hybrid living behavior (between conventional and living free‐radical polymerization) of various degrees depending on the molecular structure of the initial RAFT agent. In addition, DCHI was polymerized via ATRP with a CuCl/methyl benzoate/N,N,N′,N″,N″‐pentamethyldiethylenetriamine/cyclohexanone system at 60 °C. Both the ATRP and RAFT polymerization of the hindered monomers displayed living characteristics; however, broader than expected molecular weight distributions were observed for the RAFT systems (polydispersity index = 1.15–3.35). To assess the cause of this broadness, chain‐transfer‐to‐monomer constants for DMI, DBI, and DCHI were determined (1.4 × 10^?3, 1.3 × 10^?3, and 1.0 × 10^?3, respectively) at 60 °C. Simulations carried out with the PREDICI program package suggested that chain transfer to monomer contributed to the broadening process. In addition, the experimental results indicated that viscosity had a pronounced effect on the broadness of the molecular weight distributions. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3692–3710, 2006     

Iron‐based catalysts bearing bis(imido)–pyridine ligands for the polymerization of tert‐butyl acrylate

Iron(II) dichloride complexes bearing a tridentate nitrogen donor ligand were investigated for the homopolymerization of tert‐butyl acrylate after activation with methylaluminoxane. Two new complexes were synthesized, 2,6‐bis[1‐(cyclohexylimido)ethyl]pyridine iron chloride (FeCl₂) and 2,6‐bis[1‐(isopropylimido)ethyl]pyridine FeCl₂, and the single‐crystal X‐ray structure of the latter one was determined. Turnover frequencies of the catalysts during polymerization ranged from 36 to 241 cycles/mol/h. The obtained polymers exhibited weight‐average molecular weights ranging from 24,000 to 438,500 g/mol, and the molar mass distribution varied between 1.8 and 4.3. Activity of the catalytic system and the molar mass of the polymer are influenced by the ligand structure of the complexes as well as other polymerization conditions such as monomer concentration and temperature. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1380–1389, 2003     

Syntheses and properties of novel fluorinated polyamides based on a bis(ether‐carboxylic acid) or a bis(ether amine) extended from bis(4‐hydroxyphenyl)phenyl‐2,2,2‐trifluoroethane

Two series of novel fluorinated aromatic polyamides were prepared from 1,1‐bis[4‐(4‐carboxyphenoxy)phenyl]‐1‐phenyl‐2,2,2‐trifluoroethane with various aromatic diamines or from 1,1‐bis[4‐(4‐aminophenoxy)phenyl]‐1‐phenyl‐2,2,2‐trifluoroethane with various aromatic dicarboxylic acids with the phosphorylation polyamidation technique. These polyamides had inherent viscosities ranging from 0.51 to 1.54 dL/g that corresponded to weight‐average and number‐average molecular weights (by gel permeation chromatography) of 36,200–80,000 and 17,200–64,300, respectively. All polymers were highly soluble in aprotic polar solvents, such as N‐methyl‐2‐pyrrolidone and N,N‐dimethylacetamide, and some could even be dissolved in less‐polar solvents like tetrahydrofuran. The flexible and tough films cast from the polymer solutions possessed tensile strengths of 76–94 MPa and initial moduli of 1.70–2.22 GPa. Glass‐transition temperatures (T_g's) and softening temperatures of these polyamides were observed in the range of 185–268 °C by differential scanning calorimetry or thermomechanical analysis. Decomposition temperatures (T_d's) for 10% weight loss all occurred above 500 °C in both nitrogen and air atmospheres. Almost all the fluorinated polyamides displayed relatively higher T_g and T_d values than the corresponding nonfluorinated analogues. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 420–431, 2003     

Reactive blending of poly(ethylene 2,6-naphthalate) and Vectra A

In situ composites based on poly(ethylene 2,6-naphthalate) (PEN) and a thermotropic liquid crystal polymer (Vectra A950) were prepared by melt blending under different processing conditions. Thermal behaviour, mechanical and physical properties and morphology of the blends were investigated. The DSC analysis indicates that, as expected, Vectra enhances the crystallization process of PEN. Moreover, mechanical and thermal tests evidence the significant role of 20 wt% Vectra on increasing the material performances; tensile properties, coupled with SEM, show that strength and modulus of PEN are significantly improved when Vectra domains are long and continuous fibrils. The overall results can be attributed to the compatibilisation of the system induced by the mixing conditions that affect the extent of transreactions occurring in the melt. To deepen this aspect, the soluble and insoluble fractions in a PEN solvent were isolated and thoroughly characterized: both the fractions contain PEN/Vectra copolymers. The results underline the potentiality of the PEN/Vectra system for different high-performance applications requiring superior strength and modulus, heat stability or barrier properties.     

Atomic Oxygen Concentration in a Flowing Post-Discharge Reactor

Concentration of neutral oxygen atoms in the flowing post-discharge of a pure oxygen microwave discharge at different experimental conditions was determined with a nickel catalytic probe. The post-discharge reactor was setup for metal surface cleaning. It worked at the pressure between 20 and 100 Pa and at output power of the microwave plasma generator between 80 and 150 W. At those experimental conditions the O-atom density was found to be of the order of 10²¹ m^–3. It increased both with increasing pressure and microwave power. The degree of dissociation of oxygen molecules, on the other hand, decreased with increasing pressure.     

Batch emulsion copolymerization of 3‐O‐methacryloyl‐1,2:5,6‐di‐O‐isopropylidene‐α‐D‐glucofuranose and butyl acrylate: Synthesis and properties of the sugar latices

To obtain new polymer latices based on sugar derivative, batch emulsion copolymerizations of 3‐O‐methacryloyl‐1,2:5,6‐di‐O‐isopropylidene‐α‐D ‐glucofuranose (3‐MDG) and n‐butyl acrylate (BA) were carried out at 70 °C, with potassium persulfate as the initiator. 3‐MDG polymerizes faster than BA because of its higher reactivity ratio, r_(3‐MDG) = 1.94 versus r_(BA) = 0.54. The effect of the initial monomer composition on the polymerization rate and the thermal properties of the end copolymers was investigated. The overall rate of polymerization increases by enhancing the sugar content in the initial monomer composition. The glass‐transition temperature is linearly related to the sugar content in the copolymer. The influence of the type of surfactant showed that the particle size increases by changing from ionic to nonionic surfactant. Furthermore, the effect of the added acrylic acid (AA) on the rheological properties suggests that the sugar latices exhibit different non‐Newtonian flows depending on the pH of the latex and on the AA concentration on the particle surface. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 788–803, 2003     

Efficient route to well‐characterized homo,block, and statistical polymers containing terpyridine in the side chain

The incorporation of metal–ligand interactions into macromolecules imparts to them unique and potentially useful properties. We report the synthesis of homo, block, and statistical copolymers with controlled molecular weights, compositions, and relatively narrow polydispersities via atom transfer radical polymerization that contain activated esters for the subsequent incorporation of terpyridine. This approach is universal and allows facile access to macromolecules with rich chemical functions, illustrated here with metal ligands. Comonomers include methyl, n‐butyl, and poly(ethylene glycol) methyl ether methacrylate as well as styrene. The addition of lanthanide ions to the final copolymers generates emissive materials with blue, green, red, or purple light, depending on the metal used. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5831–5843, 2005     

A new controllable approach to synthesize hyperbranched poly(siloxysilanes)

A new controllable approach to synthesize hyperbranched poly(siloxysilanes) via hydrosilylation of A₂‐ and B′B_x‐type monomers was developed in this work. A₂ monomers (dimethylbis(dimethylsiloxy)siloxane and tetramethyldisiloxane), B′B_x monomers (methylvinyldiallylsilane and vinyltriallylsilane), and the resultant hyperbranched poly(siloxysilanes) were well characterized using FTIR, ¹H NMR, ¹³C NMR, ²⁹Si NMR, and SEC/MALLS. The In situ FTIR results indicate that the controllable polymerization can be carried out quickly and the reaction process was obviously performed in two stages. At the first stage, silicon hydride selectively reacts with vinyl silane groups, which produces intermediate structures with one Si? H and two (or three) allyl groups. Consequently, at the second stage, these intermediates act as new AB₂ (or AB₃) type monomers and continue to be self‐polymerized to generate hyperbranched polymers. By this novel controllable approach, molecular weights and their polydispersity of the resulted hyperbranched poly(siloxysilanes) can be conveniently regulated via adjusting the process parameters, such as feeding ratio of two monomers. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2708–2720, 2008     

Synthesis and copolymerization of fluorinated monomers bearing a reactive lateral group. XX. Copolymerization of vinylidene fluoride with 4‐bromo‐1,1,2‐trifluorobut‐1‐ene

The radical copolymerization of vinylidene fluoride (VDF) with 4‐bromo‐1,1,2‐trifluorobut‐1‐ene (C₄Br) was examined. This bromofluorinated alkene was synthesized in three steps, which started with the addition of bromine to chlorotrifluoroethylene. In contrast to the ethylenation of 1,1‐difluoro‐1,2‐dibromochlorethane, which failed, that of 2‐chloro‐1,1,2‐trifluoro‐1,2‐dibromoethane was optimized and led to 2‐chloro‐1,1,2‐trifluoro‐1,4‐dibromobutane. The kinetics of the copolymerization of VDF with this brominated monomer initiated by t‐butyl peroxypivalate led to an assessment of the reactivity ratios, r_VDF = 0.96 ± 0.67 and r_C4Br = 0.09 ± 0.63, at 50 °C. The suspension copolymerization was also carried out, and the chemical modifications of the resulting bromo‐containing poly(vinylidene fluoride)s were attempted and consisted mainly of elimination or nucleophilic substitution of the bromine. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 917–935, 2005