Radical co-polymerization of diiminedibromidenickel(II)-functionalized olefin with styrene: synthesis of polymer-incorporated nickel(II) alpha-diimine catalysts for ethylene polymerization

alpha-Diimine nickel catalyst hearing two allyl groups [ArN=C](2)C10H6NiBr2 (Ar = 4-allyl-2,6-(i-Pr)(2)C6H2)] (Cat-I) has been synthesized and characterized. The corresponding polymer-incorporated nickel catalysts PC and the SiO2-supported shell-core structure catalyst SC-1 were obtained by the co-polymerization of the olefin groups of Cat-1 with styrene in the presence of a radical initiator. Radical co-polymerizations with styrene in Solution were investigated in detail, and the compositions and molecular weight of the copolymers were determined. All three types of catalysts (Cat-1, PC and SC-1) have been investigated for ethylene polymerization. These catalysts were found to exhibit high activity in the presence of modified methylaluminoxane (MMAO) as a co-catalyst. Among them, the polymer-incorporated PC and SiO2 shell-core catalyst SC-1 displayed very high activity (similar to2.62 and similar to1.11 kg (mmol Ni)(-1) h(-1), respectively) with product molecular weights (M,) in the range 26 x 10(4) to 47 x 10(4) under 0.1 MPa ethylene pressure. The particle morphology of polyethylene produced by the shell-core structure catalyst SC-1 was improved.

含烯丙基席夫碱ⅣB族的金属烯烃聚合催化剂的合成、结构、高分子化及其催化乙烯聚合反应

制备出两类含烯丙基席夫碱的ⅣB族配合物[R(N=CH鄄C6H3(3鄄R)O)2MCl2(R=Allyl;R'=Pheny;M=Ti(6),M=Zr(7);R=tert鄄Butyl;R'=Allyl;M=Ti(8);M=Zr(9)),配合物(7)的单晶结构显示围绕中心金属的配合构型为畸变八面体,其中2个氯原子处于顺式位置。配合物(7,9)中的烯丙基与苯乙烯共聚可得到高分子化烯烃聚合催化剂(PSC1;PSC2)。在助催化剂(MMAO)存在下,配合物9和相应的高分子化催化剂(PSC2)显示出很高的催化乙烯聚合的活性。

Effects of chain flexibility on polymer conformation in dilute solution studied by lattice Monte Carlo simulation

Effects of chain flexibility on the conformation of homopolymers in good solvents have been investigated by Monte Carlo simulation. Bond angle constraint coupled with persistence length of polymer chains has been introduced in the modified eight-site bond fluctuation simulation model. The study about the effects of chain flexibility on polymer sizes reveals that the orientation of polymer chains under confinement is driven by the loss of conformation entropy. The conformation of polymer chains undergoing a gradual change from spherical iso-diametric ellipsoid to rodlike iso-diametric ellipsoid with the decrease of polymer chain flexibility in a wide region has been clearly illustrated from several aspects. Furthermore, a comparison of the freely jointed chain (FJC) model and the wormlike chain (WLC) model has also been made to describe the polymer sizes in terms of chain flexibility and quasi-quantitative boundary toward the suitability of the models.

Crosslinkable poly(propylene carbonate): High-yield synthesis and performance improvement

A crosslinking strategy was used to improve the thermal and mechanical performance of poly(propylene carbonate) (PPC): PPC bearing a small moiety of pendant C=C groups was synthesized by the terpolymerization of allyl glycidyl ether (AGE), propylene oxide (PO), and carbon dioxide (CO2). Almost no yield loss was found in comparison with that of the PO and CO2 copolymer when the concentration of AGE units in the terpolymer was less than 5 mol %. Once subjected to UV-radiation crosslinking, the crosslinked PPC film showed an elastic modulus 1 order of magnitude higher than that of the uncrosslinked one. Moreover, crosslinked PPC showed hot-set elongation at 65 degrees C of 17.2% and permanent deformation approaching 0, whereas they were 35.3 and 17.2% for uncrosslinked PPC, respectively. Therefore, the PPC application window was enlarged to a higher temperature zone by the crosslinking strategy.

Direct patterning of negative nanostructures on self-assembled monolayers of 16-mercaptohexadecanoic acid on Au(111) substrate via dip-pen nanolithography

Both bare and self-assembled monolayer (SAM) protected gold substrate could be etched by allyl bromide according to atomic force microscopy (AFM), x-ray photoelectron spectroscopy (XPS) and inductively coupled plasma mass spectrometric (ICPMS) analysis results. With this allyl bromide ink material, negative nanopatterns could be fabricated directly by dip-pen nanolithography (DPN) on SAMs of 16-mercaptohexadecanoic acid (MHA) on Au(111) substrate. A tip-promoted etching mechanism was proposed where the gold-reactive ink could penetrate the MHA resist film through tip-induced defects resulting in local corrosive removal of the gold substrate. The fabrication mechanism was also confirmed by electrochemical characterization, energy dispersive spectroscopy (EDS) analysis and fabrication of positive nanopatterns via a used DPN tip.

Titanium complexes with novel triaryl-substituted phosphinimide ligands: Synthesis, structure and ethylene polymerization behavior

A series of titanium phosphinimide complexes [Ph2P(2-RO-C6H4)(2)TiCl2 (7, R = CH3; 8, R = CHMe2) and (PhP(2-Me2CHOC6H4)][THF]TiCl3 (9) have been prepared by reaction of TiCl4 with the corresponding phosphinimines under dehalosilylation. The structure of complex 9 has been determined by X-ray crystallography, and a solvent molecule THF was found to be coordinated with the central metal and the Ti-O bond was consistent with the normal Ti-O (donor) bond length. The complexes 7 and 8 displayed inactive to ethylene polymerization, and the complex 9 displayed moderate activity in the presence of modified methylaluminoxane (MMAO) or i-BU3Al/Ph3CB(C6F5)(4), and this should be partly attributed to coordination of THF with titanium and the steric effect of two iso-propoxyl. And catalytic activity up to 32.2 kg-PE/(mol-Ti h bar) was observed.

Differential proteomic analysis of neonatal cardiomyocytes in response to beta-adrenergic receptor stimulation

beta-Adrenoceptors(beta-ARs) play a critical role in regulating cardiac functions under both physiological and pathological conditions. To further explore the mechanisms through which beta-ARs perform its actions, proteomic approaches were adopted to study the global protein patterns in cultured neonatal rat cardiomyocytes exposed to isoproterenol (ISO). A modified method, "Mirror Images in One Gel", was used to improve the reproducibility and resolution power of two-dimensional electrophoresis. A 2-DE map with a good reproducibility was obtained in which 1281 70 spots were detected and about 1191 +/- 54 spots were matched, with an average matching rate of 92.9%. Nine proteins with significant changes were identified by using peptide mass fingerprinting(PMF) data obtained via MALDI-MS.

Reactive compatibilization of polyamide 6 with isocyanate functionalized ethylene-propylene copolymer

Reactive compatibilization of ethylene-propylene copolymer functionalized with allyl (3-isocyanato-4-tolyl) carbamate (TAI) isocyanate (EPM-g-TAI) and polyamide 6 (PA6) was investigated in this paper, FTIR analysis revealed the evidence of a chemical reaction between the end groups of PA6 and EPM-g-TAI. Thermal, rheological, morphological, and mechanical properties of the resultant system were examined, DSC analysis indicated that the crystallization of PA6 in Pa6/EPM-g-TAI blends was inhibited, due to the chemical reaction that occurs at the interface of PA6 and EPM-g-TAI. Rheological measurement showed that complex viscosity and storage modulus of PA6/EPM-g-TAI were both dramatically enhanced compared to those of PA6/EPM at the same blending composition. After examining the morphology of both blending systems, smaller particile sizes, more homogeneous distribution of domains and improved interfacial adhesion between matrix and domains were observed in the compatibilized system. Mechanical properties such as tensile strength. Young's modulus, flexural strength and modulus, as well as notched and un-notched impact strength of PA6/EPM-g-TAI blends were also found to improve gradually with increasing the content of grafted TAI.

Cationic cyclization of neoprene with a diethylaluminum chloride and organic chloride catalyst system

The cyclization of neoprene was achieved with the aid of a cationic catalyst system based on diethylaluminum chloride (Et2AlCl) and an organic chloride, allyl chloride (CH2=CHCH2Cl) or benzyl chloride (C6H5CH2Cl). The main parameters of the cyclization process were investigated. Elastomers with low intrinsic viscosity, ready solubility and some gelling were obtained. Xylene was a good solvent for the cyclization process, which took place in a very short time (less than or equal to5 min). The products were characterized with IR, H-1-NMR, differential scanning calorimetry, and gel permeation chromatography. The polycyclic structure was determined. The degree of cyctization and the incorporated solvent content were estimated with a H-1-NMR method.

Polymer immobilized silane bridged metallocene catalysts for ethylene polymerization

Ansa-zirconocene complex with an allyl substituted silane bridge [(CH2=CHCH2)CH3Si(C5H4)(2)]ZrCl2 (1a) has been synthesized and characterized. The molecular structure of la has been determined by X-ray crystallographic analysis. The polymer immobilized metallocene catalyst 1b is prepared by the co-polymerization of la with styrene in the presence of radical initiator. The result of ethylene polymerization showed that the polymer immobilized metallocene catalyst kept high activity for ethylene polymerization and was a potential supported catalyst for olefin polymerization.

Resonance Raman spectroscopic study of cytochrome c mutants

The spectroscopic characteristics of cytochrome c(WT) and its mutants(Y67F and N521) in the low frequency region were studied by Resonance Raman technique. The results show that the replacement of phenylalanine for Tyr 67 in WT had a very slight effect on the hydrogen-bonding and conformation of the amino acid residues around propionic acid side chains of heme group. However, large effects on the hydrogen-bonding of internal water with its surrounding amino acid residues and hydrophobility of the home cavity were observed as Asn 52 was substituted with isoleucine, which resulted in conformational regulations of home group and surrounding amino acid residues.

Polymerized unsymmetrical iron post-metallocene catalyst for ethylene polymerization

The unsymmetrical allyl containing post-metallocene complex [ArN = C( Me)] [(ArN)-N-' = C(Me)]C5H3NFeCl2 [Ar = 2,6(i- Pr)(2)C6H3, Ar' = 4-allyl-2,6-(i-Pr)(2)C6H3] (3) has been prepared and characterized. Complex (3) can be co-polymerized with styrene in the presence of radical initiator to produce polymerized post-metallocene catalyst which exhibits high activity for ethylene polymerization (2.5 x 10(6) g PE/mol Fe.h).

Circular dichroism and resonance Raman comparative studies of wild type cytochrome c and F82H mutant

The UV-visible, circular dichroism (CD), and resonance Raman (RR) spectra of the wild type yeast iso-1-cytochrome c (WT) and its mutant F82H in which phenylalanine-82 (Phe-82) is substituted with His are measured and compared for oxidized and reduced forms. The CD spectra in the intrinsic and Soret spectral region, as well as RR spectra in high, middle, and low frequency regions, are discussed. From the analysis of the spectra, it is determined that in the oxidized F82H the two axial ligands to the heme iron are His-18 and His-82 whereas in the reduced form the sixth ligand switches from His-82 to Met-80 providing the coordination geometry similar to that of WT. Based on the spectroscopic data, the conclusion is that the porphyrin macrocycle is less distorted in the oxidized F82H compared to the oxidized WT. Similar distortions are present in the reduced form of the proteins. Frequency shifts of Raman bands, as well as the decrease of the or-helix content in the CD spectra, indicate more open conformation of the protein around the heme. (C) 2000 John Wiley & Sons, Inc.

Mechanical relaxation time of comblike polymer electrolyte

Using poly(styrene-co-maleic anhydride) as the backbone and poly(ethylene glycol) methyl ether as side chains,three kinds of comblike polymers of different side chain length were synthesized. The Li-salt complexes and their firms were prepared. The dynamic mechanical properties were investigated. It was found that the main chain was rigid and the side chain was flexible in this comblike polymer system. Based on the time-temperature equivalence principle, a master curve was constructed. By selecting T-alpha as reference temperature, Arrhenius plots of shift factor and iso-free-volume plots were attained. The values of WLF parameters C-1 and C-2 increase with increasing salt concentration. By reference to T-0 = 50 degrees C, the relation between the average relaxation time 1g tau(c) and Li-salt concentration C is linear. The master curves are displaced progressively to higher frequencies as the M-w of side chains is increased. The relation between the average relaxation time 1g tau(n) and M-w of side chains is also linear. And the master curves are movable with the change of salts. It shows the effect of different kinds of salt on relaxation time.

Studies on the alkylation of isobutane with butene over WO3/ZrO2 strong solid acid (I) - Effect of preparation, load of WO3 and calcination temperature

A series of WO3/ZrO2 strong solid acid prepared under different conditions were studied. Their crystal structures, surface properties and acidities were determined by means of XRD, DTA-TG, H-2- TPR, Laser Raman and acidity measurements. The results revealed that ZrO2 in WO3/ZrO2 existed mainly in tetragonal phase, the addition of WO3 plays an important role to stabilize tetragonal phase of ZrO2 and thus the catalyst had a considerable surface area. WO3 in WO3/ZrO2 was dispersed and crystalized in WO3 crystalite on ZrO2 surface and partly reacted with ZrO2 to form the bond of Zr-O-W, which acts as the strong solid acid site. The catalytic properties of WO3/ZrO2 strong solid acid for alkylation of iso-butane with butene under the different conditions were investigated. They had a better reaction performance than other strong solid acids, a parallel relationship could be drawn between the catalytic activity and the amount of acid sites as well as the acidic strength of the catalysts.