Preparation and application of a novel core-shell-particle-supported zirconocene catalyst

The use of functional groups bearing silica/poly(styrene-co-4-vinylpyridine) core-shell particles as a support for a zirconocene catalyst in ethylene polymerization was studied. Several factors affecting the behavior of the supported catalyst and the properties of the resulting polymer, such as time, temperature, Al/N (molar ratio), and Al/Zr (molar ratio), were examined. The conditions of the supported catalyst preparation were more important than those of the ethylene polymerization. The state of the supported catalyst itself played a decisive role in both the catalytic behavior of the supported catalyst and the properties of polyethylene (PE). IR and X-ray photoelectron spectroscopy were used to follow the formation of the supports. The formation of cationic active species is hypothesized, and the performance of the core-shell-particle-supported zirconocene catalyst is discussed as well. The bulk density of the PE formed was higher than that of the polymer obtained from homogeneous and polymer-supported Cp2ZrCl2/methylaluminoxane catalyst systems. (C) 2001 John Wiley & Sons, Inc.

Synthesis and metallophilic properties of troponoid thiocrown ethers

A new class of ionophores with troponoid and thiocrown ether units was prepared. Cation-binding properties of troponoid dithiocrown ethers were characterized using UV and NMR spectroscopies. They have affinity with metal ions; in particular, they showed high affinity with Hg2+. Transport of Hg2+ through a CHCl3 liquid membrane with troponoid dithiocrown ethers was examined in a U-type cell. From an aqueous solution of HgCl2 and CuCl2, Hg2+ is transferred selectively and smoothly, while the Cu2+ remained quantitatively in the original solution. The cavity size of dithiocrown ethers is one of the requirements for effective extraction and transport of Hg2+. However, derivatives with a smaller cavity still extract and transport Hg2+. A polymer-supported troponoid dithiocrown ether was prepared to transport Hg2+ effectively and repeatedly. Comparing the troponoid dithiocrown ether with the benzenoid dithiocrown ether with a similar cavity size, the former was more effective for the transport of Hg2+. It is proposed that the tropone ring assisted the release of Hg2+ from the complex by Coulomb repulsion between the protonated tropone ring and Hg2+.

Synthesis, characterization and catalytic properties of chiral BINOL functionalized mesoporous silicas for enantioselective Morita-Baylis-Hillman reaction

Several Chiral BINOL functionalized mesoporous silicas were prepared by post grafting of organosilane derivatives of (S)-BINOL (1,1'-bi-2-naphthol) on SBA-15 and characterized by C-13 CP/MAS NMR, FT-IR, UV-visible absorption spectra, elemental analysis, powder XRD, nitrogen adsorption-desorption isotherms and TEM techniques. Their catalytic properties were demonstrated in enantioselective Morita-Baylis-Hillman reaction of 3-phenylpropanal and cyclohexenone.

Liquid-phase hydrogenation of furfural to tetrahydrofurfuryl alcohol catalyzed by polymer resin supported palladium catalysts

Three kinds of polymer resin supported Pd catalysts were prepared by mixing PdCl2, with alkaline styrene anion exchange resins[D392 -NH2, D382, -NHCH3, D301R, -NH(CH3)(2)], strongly alkaline styrene anion exchanged resin [201 X 7DVB, -NH+ (CH3)(3)] and alkaline epoxy exchange resin (701, -NH2), and hydrogenating in liquid phase at 1.013 X 10(5) Pa. The hydrogenation of furfural was studied under the reaction conditions such as solvent, temperature. Pd content in the supported catalyst and the amount of the catalyst. The yield of hydrogenation reaction of furfural markedly increased to 100% and the selectivity to tetrahydrofurfuryl alcohol increased to over 98% by polymer (alkaline styrene anion exchange resins D392, -NH2, D382, -NHCH3) supported palladium catalysts comparing with the yield over 70% and selectivity over 97% by palladium catalyst, in 50% alcohol-50% water or pure water solution at 1.013 X 10(5) Pa. The relationship between hydrogenation and the structures of functional group in the supporting resin was examined by XPS method.

Enhanced Proton Conduction in Polymer Electrolyte Membranes as Synthesized by Polymerization of Protic Ionic Liquid-Based Microemulsions

Proton-conducting membranes were prepared by polymerization of microemulsions consisting of surfactant-stabilized protic ionic liquid (PIL) nanodomains dispersed in a polymerizable oil, a mixture of styrene and acrylonitrile. The obtained PIL-based polymer composite membranes are transparent and flexible even though the resulting vinyl polymers are immiscible with PIL cores. This type of composite membranes have quite a good thermal stability, chemical stability, tunability, and good mechanical properties. Under nonhumidifying conditions, PIL-based membranes show a conductivity up to the order of 1 x 10(-1) S/cm at 160 degrees C, due to the well-connected PIL nanochannels preserved in the membrane. This type of polymer conducting membranes have potential application in high-temperature polymer electrolyte membrane fuel cells.

Influence of interface modification on the performance of polymer/Bi2S3 nanorods bulk heterojunction solar cells

In this paper, bulk heterojunction photovoltaic devices based on the poly[2-methoxy-5-(3',7'-dimethyloctyloxy)- 1,4-phenylenevinylene] (MDMO-PPV):Bi2S3 nanorods hybrid material were present. To optimize the performance of the devices, the interface modification of the hybrid material that has a significant impact on the exciton dissociation efficiency was studied. An improvement in the device performance was achieved by modifying the Bi2S3 surface with a thin dye layer. Moreover, modifying the Bi2S3 surface with anthracene-9-carboxylic acid can enhance the performance further. Compared with the solar cells with Bi2S3 nanorods hybrid with the MDMO-PPV as the active layer, the anthracene-9carboxylic acid modified devices are better in performance, with the power conversion efficiency higher by about one order in magnitude.

Isoprene polymerization with indolide-imine supported rare-earth metal alkyl and amidinate complexes

Reaction of 7-{(N-2,6-R)iminomethyl)}lindole (HL1, R = dimethylphenyl; HL2, R = diisopropylphenyl) and rare-earth metal tris(alkyl)s, Ln(CH2SiMe3)(3)(THF)(2), generated new rare-earth metal bis(alkyl) complexes LLn(CH2SiMe3)(2)(THF) [L = L-1: Ln = Lu. (1a), Sc (1b); L = L-2 : Ln = Lu (3a), Se (3b)] and mono(alkyl) complexes L-2 Lu-2(CH2SiMe3) (4a). Treatment of alkyl complexes 1a and 4a with N,N'-diisopropylcarbodiimide afforded the corresponding amidinates (LLu)-Lu-1{iPr(2)NC(CH2SiMe3) NiPr2}(2) (2a) and L-2 Lu-2{iPr(2)NC(CH2SiMe3)NiPr2} (5a), respectively.

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.

Effects of polar group saturation on physical gelation of Amphiphilic polymer solutions

Monte Carlo simulation on the basis of the comblike coarse grained nonpolar/polar (NP) model has been carried out to study the polar group saturation effect on physical gelation of amphiphilic polymer solutions. The effects of polar group saturation due to hydrogen bonding or ion bridging on the sol-gel phase diagram, microstructure of aggregates, and chain conformation of amphiphilic polymer solutions under four different solvent conditions to either the nonpolar backbone or the polar side chain in amphiphilic polymer chains have been investigated. It is found that an increase of polar group saturation results in a monotonically decreased critical concentration of gelation point, which can be qualitatively supported by the dynamic theological measurements on pectin aqueous solutions. Furthermore, various solvent conditions to either the backbone or the side chain have significant impact on both chain conformation and microstructure of aggregates. When the solvent is repulsive to the nonpolar backbone but attractive to the polar side chain, the polymer chains are collapsed, and the gelation follows the mechanism of colloidal packing; at the other solvent conditions, the gelation follows the mechanism of random aggregation.

Synthesis and characterization of polyethylene/clay-silica nanocomposites: A montmorillonite/silica-hybrid-supported catalyst and in situ polymerization

A novel approach to the preparation of polyethylene (PE) nanocomposites, with montmorillonite/silica hybrid (MT-Si) supported catalyst, was developed. MT-Si was prepared by depositing silica nanoparticles between galleries of the MT. A common zirconocene catalyst [bis(cyclopentadienyl)zirconium dichloride/methylaluminoxane] was fixed on the MT-Si surface by a simple method. After ethylene polymerization, two classes of nanofillers (clay layers and silica nanoparticles) were dispersed concurrently in the PE matrix and PE/clay-silica nanocomposites were obtained. Exfoliation of the clay layers and dispersion of the silica nanoparticles were examined with transmission electron microscopy. Physical properties of the nanocomposites were characterized by tensile tests, dynamic mechanical analysis, and DSC. The nanocomposites with a low nanofiller loading (<10 wt %) exhibited good mechanical properties. The nanocomposite powder produced with the supported catalyst had a granular morphology and a high bulk density, typical of a heterogeneous catalyst system.

Zirconocene catalyst well spaced inside modified montmorillonite for ethylene polymerization: role of pretreatment and modification of montmorillonite in tailoring polymer properties

Zirconocene catalyst was heterogenized inside an organosilane-modified montmorillonite (MMT) pretreated by calcination and acidization, for supported catalyst systems with well-spaced alpha-olefin polymerization active centers. The varied pretreatment and modification conditions of montmorillonite are efficient for supported zirconocene catalysts in control of polyethylene microstructures, in particular, molecular weight distribution. In contrast to other supported catalyst systems, Cp2ZrCl2/modified montmorillonite(MMT-7)-supported catalysts with a distinct interlayer structure catalyzed ethylene homopolymerization and copolymerization with I-octene activated by methylaluminoxane (MAO), resulting in polymers with a bimodal molecular weight distribution (MWD).