Effect of annealing on the deformation mechanism of a styrene/n-butyl acrylate copolymer latex film investigated by synchrotron small-angle X-ray scattering

The deformation mechanism of a styrene/n-butyl acrylate copolymer latex film subjected to uniaxial tensile stress was studied by small-angle X-ray scattering. The influence of annealing at 23, 60, 80, and 100 degrees C for 4 h on microscopic deformation processes was elucidated. It was demonstrated that the microscopic deformation mechanism of the latex films transformed gradually from nonaffine deformation behavior to affine deformation behavior with increasing annealing temperature.

Branched polystyrene with abundant pendant vinyl functional groups from asymmetric divinyl monomer

Branched polystyrenes with abundant pendant vinyl functional groups were prepared via radical polymerization of an asymmetric divinyl monomer, which possesses a higher reactive styryl and a lower reactive butenyl. Employing a fast reversible addition fragmentation chain transfer (RAFT) equilibrium, the concentration of active propagation chains remained at a low value and thus crosslinking did not occur until a high level of monomer conversion. The combination of a higher reaction temperature (120 degrees C) and RAFT agent cumyl dithiobenzoate was demonstrated to be optimal for providing both a more highly branched architecture and a higher polymer yield.

Polymerization of ethylene to branched polyethylene with silica and Merrifield resin supported nickel(II) catalysts with alpha-diimine ligands

Silica and Merrifield resin were used as carriers for the support of alpha-diimine nickel(II) precatalysts for ethylene polymerization. The alpha-diimine ligands containing allyl were modified by introducing the reactive Si-Cl end-group, allowing their immobilization via a direct reaction of the Si-Cl groups with the silanols on silica surface or the hydroxyls on the ethanolamine-modified Merrifield resin. The resulting supported alpha-diimine ligands were characterized by analytical and spectroscopic techniques (NMR and Fr-IR).

Living polymerization of 1,3-butadiene by a Ziegler-Natta type catalyst composed of iron(III) 2-ethylhexanoate, triisobutylaluminum and diethyl phosphite

Living characteristics of facilely prepared Ziegler-Natta type catalyst system consisting of iron(III) 2-ethylhexanoate, triisobutylaluminum and diethyl phosphite have been found in the polymerization of 1,3-butadiene in hexane at 40 degrees C. The characteristics have been well demonstrated by: a first-order kinetics with respect to monomer conversion, a narrow molecular weight distribution (M-w/M-n = 1.48-1.52) of polybutadiene in the entire range of polymerization conversion and a good linearity between M-n and the yield of polymer. Feasible post-polymerization of 1,3-butadiene and block co-polymerization of 1,3-butadiene and isoprene further support the living natures of the catalyst bestowed with.

Metal dependent control of cis-/trans-1,4 regioselectivity in 1,3-butadiene polymerization catalyzed by transition metal complexes supported by 2,6-bis[1-(iminophenyl)ethyl]pyridine

Fe(III), Cr(III), Fe(II), Co(II) and Ni(II) chloride complexes supported by 2,6-bis[1-(iminophenyl)ethyl]pyridine have been synthesized and characterized along with single crystal X-ray diffraction. These complexes, in combination with MAO, have been examined in butadiene polymerization. The catalytic activity and regioselectivity are strongly controlled by metal center and cocatalyst (MAO/Co ratio dependent in the case of Co(II) complex). The activity decreases in the order of Fe(III) > Co(II) > Cr(III) approximate to Ni (II) complexes, in consistent with the space around the metal center. Polybutadiene with different microstructure content, from high trans-1,4 units (88-95% for iron(III) and Cr(III)), medium trans-1,4 and cis-1,4 units (55% and 35%, respectively, for iron(II)) to high cis-1,4 units 79% for Co(II) and 97% for Ni(II) call be easily achieved by varying of the metal center.

Microstructure and Deformation Behavior of Polyethylene/Montmorillonite Nanocomposites with Strong Interfacial Interaction

Deformation behavior of polyethylene/modified montmorillonites with polymerizable surfactant (PE/P-MMT) nanocomposite with strong interfacial interaction was studied by means of morphology observation and X-ray scattering measurements. The orientation of PE chains was accompanied by the orientation of well-dispersed MMT platelets due to the presence of strong interfacial interaction, and both of the orientations were parallel to the deformation direction. The high degree of orientation of MMT platelets and PE chains resulted from the synergistic movement of PE matrix and MMTs, which originated from the presence of a network-like structure.

Composition effect on dewetting of ultrathin films of miscible polymer blend

Two kinds of dewetting and their transition induced by composition fluctuation due to different composition in blend [poly(methyl methacrylate) (PMMA) and poly(styrene-ran-acrylonitrile) (SAN)] films on SiOx substrate at 145 degrees C have been studied by in-situ atomic force microscopy (AFM). The results showed that morphology and pathway of dewetting depended crucially on the composition. Possible reason is the variation in intensity of composition fluctuation resulted from the change of components in polymer blend. Based on the discussion of this fluctuation due to the composition gradient, parameter of U-q0/E, which describes the initial amplitude of the surface undulation and original thickness of film respectively, has been employed to distinguish the morphologies of spontaneous dewetting including bicontinuous structures and holes.

Microphase Separation of Mixed Polymer Brushes: Dependence of the Morphology on Grafting Density, Composition, Chain-Length Asymmetry, Solvent Quality, and Selectivity

Microphase separation of binary mixed A/B polymer brushes exposed to different solvents is studied using Single-Chain-in-Mean-Field simulations. Effects of solvent quality and selectivity, grafting density, composition, and chain-length asymmetry are systematically investigated, and diagrams of morphologies in various solvents are constructed as a function of grafting density and composition or chain-length asymmetry. The structure of the microphase segregated morphologies lacks long-range periodic order, and it is analyzed quantitatively Using Minkowski measures.

Synthesis and characterization of functional poly(gamma-benzyl-L-glutamate) (PBLG) as a hydrophobic precursor

Four kinds of functional poly(gamma-benzyl-L-glutamate) (PBLG) copolymers containing chloro, azido, allyl or propargyl groups on the side chains were synthesized through ester exchange reactions of PBLG with functional alcohols without any protection and de-protection process. Hydrolysis of PBLG, which was found during the ester exchange reaction under low ratios of alcohol to the repeat units of PBLG, was thoroughly investigated, and could be successfully depressed by addition of certain amount of benzyl alcohol to the reaction system. Click chemistry reactions of the azidized or propargylated copolymers, thiol-ene reaction of the allyllated copolymer were taken successfully, indicating that the functional groups on the copolymers were still reactive.

Regioselective Bis-Selenation of Allenes Catalyzed by Palladium Complexes: A Theoretical Study

The reaction mechanism of Pd(O)-catalyzed allene bis-selenation reactions is investigated by using density functional methods. The overall reaction mechanism has been examined. It is found that with the bulkier PMe3 ligand, the rate-determining step is the reductive elimination process, while allene insertion and reductive elimination processes are competitive for the rate-determining step with the PH3 ligand, indicating the importance of the ligand effect. For both cis and trans palladium complexes, allene insertion into the Pd-Se bond of the trans palladium complex using the internal carbon atom attached to the selenyl group is prefer-red among the four pathways of allene insertion processes. The formation of sigma-allyl and pi-allyl palladium complexes is favored over that of the sigma-vinyl palladium species. By using methylallene, the regioselectivity of monosubstituted allene insertion into the Pd-Se bond is analyzed.

Fabrication and characterization of microstructured and pH sensitive interpenetrating networks hydrogel films and application in drug delivery field

Novel microstructured and pH sensitive poly(acryliac acid-co-2-hydroxyethyl methacrylate)/poly(vinyl alcohol) (P(AA-co-HEMA)/PVA) interpenetrating network (IPN) hydrogel films were prepared by radical precipitation copolymerization and sequential IPN technology. The first P(AA-co-HEMA) network was synthesized in the present of IPN aqueous solution by radical initiating, then followed by condensation reaction (Glutaraldehyde as crosslinking agent) within the resultant latex, it formed multiple IPN microstructured hydrogel film. The film samples were characterized by IR, SEM and DSC. Swelling and deswelling behaviors and mechanical property showed the novel multiple IPN nanostuctured film had rapid response and good mechanical property. The IPN films were studied as controlled drug delivery material in different pH buffer solution using cationic compound, crystal violet as a model drug.

Preparation and Characterization of Nanostructured and High Transparent Hydrogel Films with pH Sensitivity and Application

Novel nanostructured, high transparent, and pH sensitive poly(2-hydroxyethyl methacrylate-co-methacryliac acid)/poly(vinyl alcohol) (P(HEMA-co-MA)/PVA) interpenetrating polymer network (IPN) hydrogel films were prepared by precipitation copolymerization of aqueous phase and sequential IPN technology. The first P(HEMA-co-MA) network was synthesized in aqueous solution of PVA, then followed by aldol condensation reaction, it formed multiple IPN nanostructured hydrogel film. The film samples were characterized by IR, SEM, DSC, and UV-vis spectrum. The transmittance arrived at 93%. Swelling and deswelling behaviors showed the multiple IPN nanostructured film had rapid response. The mechanical properties of all the IPN films improved than that of PVA film. Using crystal violet as a model drug, the release behaviors of the films were studied.

In Situ Preparation and Luminescent Properties of CeF3 and CeF3:Tb3+ Nanoparticles and Transparent CeF3:Tb3+/PMMA Nanocomposites in the Visible Spectral Range

CeF3 and CeF3:Tb3+ nanoparticles were prepared by reverse microemulsion with a functional monomer, methyl methacrylate (MMA), as the oil phase, and CeF3:Tb3+/poly (methyl methacrylate) (PMMA) nanocomposites were obtained via polymerization of the MMA monomer. The nanoparticles and nanocomposites have been well characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), low- and high-resolution transmission electron microscope (TEM), selected-area electron diffraction (SAED), thermogravimetric analysis (TGA), UV/vis transmission spectra, photoluminescence excitation, and emission spectra and luminescence decays. The well-crystallized CeF3 and CeF3:Tb3+ nanoparticles are spherical with a mean diameter of 15 nm. They show the characteristic emission of Ce3+ 5d-4f (313 nm, D-2-F-2(5/2); 323 nm, D-2-F-2(7/2)) and Tb3+ D-5(4)-F-7(J) (J = 6-3, with D-5(4)-F-7(5) green emission at 541 nm as the strongest one) transitions, respectively.

In situ preparation and luminescent properties of LaPO4:Ce3+, Tb3+ nanoparticles and transparent LaPO4:Ce3+, Tb3+/PMMA nanocomposite

LaPO4:Ce3+, Tb3+ nanoparticles were prepared by the reverse microemulsion with functional monomer, methyl methacrylate (MMA) as oil phase, and LaPO4:Ce3+, Tb3+/poly(methyl methacrylate) (PMMA) nanocomposite was obtained via polymerization of MMA monomer. The nanoparticles and nanocomposite have been well characterized by XRD, SEM, TEM, UV/vis spectrum, photoluminescence excitation and emission spectra and luminescence decays. The obtained solid nanocomposite LaPO4:Ce3+, Tb3+/PMMA is highly transparent and exhibits strong green photoluminescence upon UV excitation, due to the integration of luminescent LaPO4:Ce3+, Tb3+ nanoparticles. The luminescent lifetime of Tb3+ is determined to be 1.25 ms in the nanocomposite. (C) 2009 Elsevier Inc. All rights reserved.

Toughening effects of poly(butylene terephthalate) with blocked isocyanate-functionalized poly(ethylene octene)

BACKGROUND: Blocked isocyanate-functionalized polyolefins have great potential for use in semicrystalline polymer blends to obtain toughened polymers. In this study, poly(butylene terephthalate) (PBT) was blended with allyl N-[2-methyl-4-(2-oxohexahydroazepine-1 -carboxamido)phenyl] carbamate-functionalized poly(ethylene octene) (POE-g-AMPC).RESULTS: New peaks at 2272 and 1720 cm(-1), corresponding to the stretching vibrations of NCO and the carbonyl of NH-CO-N, respectively, in AMPC, appeared in the infrared spectrum of POE-g-AMPC. Both rheological and X-ray photoelectron spectroscopy results indicated a new copolymer was formed in the reactive blends. Compared to uncompatibilized PBT/POE blends, smaller dispersed particle sizes with narrower distribution were found in the compatibilized PBT/POE-g-AMPC blends. There was a marked increase in impact strength by about 10-fold over that of PBT/POE blends with the same rubber content and almost 30-fold higher than that of pure PBT when the POE-g-AMPC content was 25 wt%.