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  • Polymer and Materials Science  (248)
  • Analytical Chemistry and Spectroscopy  (31)
  • Animals
  • 1995-1999  (279)
  • 1
    ISSN: 0887-624X
    Keywords: dinuclear metallocene ; polysiloxane bridge ; heterogenation ; ethylene polymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of ethylene was studied by using a series of polysiloxane-bridged dinuclear zirconocenes [(SiMe2O)nSiMe2(C5H4)2][(C9H7)ZrCl2]2 (7, n = 1; 8, n = 2; 9, n = 3), the corresponding mononuclear zirconocene (C5H5)(C9H7)ZrCl2, 10, and the pentamethylene-bridged dinuclear zirconocene [(CH2)5(C5H4)2][(C9H7)-ZrCl2]2, 13. From the polymerization studies using these catalysts it was found that (i) activities of the polysiloxane dinuclear zirconocenes 7-9 wre lower than that of the corresponding mononuclear zirconocene 10, (ii) molecular weights of polyethylenes produced by the dinuclear metallocenes are greater than that of polyethylene produced by the mononuclear metallocene, (iii) the complex 9 holding the longest bridging ligand exhibited the highest activity but produced a polymer having the smallest molecular weight among the polysiloxane-bridged dinuclear zirconocenes, and (iv) the pentamethylene-bridged dinuclear metallocene 13 showed higher activity than the complexes 7-9 and the mononuclear zirconocene 10. The formation of the lowest molecular weight of polyethylene by 9 was attributed to the influence of electron withdrawal caused by the Lewis acid-base interaction between the acidic aluminum of the cocatalyst and the basic oxygen at the polysiloxane linkage as well as the lack of a steric problem. An increase in steric congestion around the metal center led to not only a decrease in catalytic activity due to preventing facile monomer access to the active site but also an increase in the molecular weight of polyethylenes due to supressing β-H elimination. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3717-3728, 1997
    Additional Material: 4 Ill.
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  • 2
    ISSN: 1022-1336
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two kinds of the trisiloxane-bridged dinuclear titanium metallocene-type complexes were synthesized. They are monocyclopentadienyl and biscyclopentadienyl dinuclear titanocenes with trisiloxane bridges. The above complexes with modified methylaluminoxane (MMAO) cocatalyst initiate the polymerizations of ethylene and styrene to produce high-density polyethylene and syndiotactic polystyrene. In addition, a copolymer of ethylene and styrene was obtained.
    Additional Material: 1 Ill.
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  • 3
    ISSN: 0887-6266
    Keywords: unsaturated polyester ; free radical polymerization ; curing kinetics ; induction time ; kinetics model ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Curing kinetics of unsaturated polyester resin system exhibiting apparent induction periods was investigated by modeling free radical initiation and propagation processes. The isothermal curing induction time as well as the maximum-rate time provided the same activation energy in the Arrhenius relation, and therefore, the isothermal curing master curve was constructed by using the reduced time method. Two model elementary rate equations for radical and monomer were proposed to describe the free radical polymerization of unsaturated polyester resin systems. The power law was adopted to express the conversion dependence function of the initiation efficiency and the monomer reaction rate. Demonstrating the capability of the developed model, the agreement between experimental and predicted data was excellent in both isothermal and dynamic-heating conditions, even with the same model parameters in different thermal conditions. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2447-2456, 1997
    Additional Material: 8 Ill.
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  • 4
    ISSN: 1022-1336
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The disiloxane-bridged zirconocene complexes, tetramethyldisiloxanediylbis (cyclopentadienyl)zirconium dichloride and tetramethyldisiloxanediylbis(cyclopentadienyl) dimethylzirconium initiate the homopolymerization of ethene as well as the copolymerization of ethene and α-olefin with a modified methylaluminoxane as cocatalyst. The catalyst systems give resonable activity but the molecular weight of polyethene decreases drastically with increasing polymerization temperature.
    Additional Material: 2 Ill.
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  • 5
    ISSN: 0887-624X
    Keywords: polyimides ; electrooptics ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aromatic polyimides with side chain nonlinear optical chromophores have been investigated through a facile two-step synthetic route. First, various poly(hydroxy imide)s have been synthesized by direct thermal imidization of diaminophenol dihydrochloride salt and aromatic dianhydride monomers. The resulting polyimides bearing phenolic hydroxy groups were found to react easily with the terminal hydroxy group on the chromophores via the Mitsunobu condensation to give corresponding polyimides with high optical nonlinearities and good solubility in common organic solvents. Detailed physical properties showed that these polyimides have a molecular weight (Mw) of 31,000 and high glass transition temperature above 220°C, ensuring a long-term alignment stability at elevated temperature. The electrooptic coefficients, r33, of the electrically poled polymer films were in the range 1.8-7.6 pm/V at 1.3 μm. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 301-307, 1998
    Additional Material: 3 Ill.
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  • 6
    ISSN: 0887-624X
    Keywords: fluorinated poly(arylene ether) ; phenyl ethynyl ; polymer optical waveguide ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Crosslinkable fluorinated poly(arylene ethers) (FPAE-Fn-PEP) with high transparency and high thermal stability have been investigated for low-loss optical waveguide materials. FPAE-Fn-PEP bearing phenyl ethynyl moiety at the polymer chain end were synthesized by the reaction of 4,4′-(hexafluoro-isopropylidene)diphenol with an excess decafluorobiphenyl, followed by the reaction of 4-phenyl ethynyl phenol. The Mns and Mw/Mns of the polymers determined by GPC with polystyrene standard were in the range of 6200 to 19,400 and 1.4 to 2.04, respectively. The resulting polymers were thermally crosslinked at 320°C for 2 h. The cured polymers show good chemical resistance and high thermal stability up to 510°C under nitrogen. The refractive indices of their films were controlled between 1.495 and 1.530 at 1.55 μm by adjusting molecular weight. A single-mode channel waveguide made of FPAE-F20-PEP was fabricated by conventional photolithography and O2 reactive ion etching (RIE). The propagation loss of the channel waveguide was measured and found to be less than 0.2 dB/cm at 1.55 μm. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2881-2887, 1998
    Additional Material: 4 Ill.
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  • 7
    ISSN: 0021-9304
    Keywords: vascular graft ; polyester ; porosity ; alginate impregnation ; blood-leak prevention ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine , Technology
    Notes: Alginate gels are known to be biocompatible, degradable, and nontoxic. In this study, sodium alginate was impregnated into a porous, knitted polyester graft (Microvel® double velour graft) 6 mm in diameter. The alginate-impregnated graft was investigated in vitro and in vivo to evaluate its potential for use as a new vascular graft impervious to blood, while retaining high porosity for tissue ingrowth and biological healing. For in vitro investigation, the coating weight, water permeability, morphology, and mechanical properties of the alginate-impregnated grafts were compared to those of control or commercially available collagen-impregnated (Hemashield®) grafts. The water permeability of the controls (1846 mL/min cm2 at 120 mm Hg) was reduced 〉99% by the alginate impregnation, rendering the graft impervious to blood. The coating weight of the alginate was 45 mg/g of graft, producing a much lower value than that of the collagen-impregnated model (310 mg/g). For in vivo investigation, the alginate-impregnated grafts were implanted in the aorta of mongrel dogs without preclotting for scheduled periods ranging from 4 h to 6 months. The control grafts after preclotting and the collagen-impregnated grafts without preclotting were also implanted for 3 and 6 months for comparison. Gross observation of the explanted grafts and histologic examination of the representative sections were conducted for three types of grafts using a light microscope after hematoxylin-eosin staining. No significant differences were observed between the histologic appearance of the alginate-impregnated grafts and that of the preclotted and collagen-impregnated grafts in terms of the degree of inflammation, foreign-body giant cell reaction, and intimal fibrosis. Endothelial-like cells were present on the midsections of all the grafts after 3 months of implantation. The resorption rate of alginate impregnated into the graft was also examined after staining the sections with periodic acid-Schiff reagent, Toluidine blue, and Alcian blue, which are specific for alginates. The staining alginate was partially visible between the graft fabrics up to 1 month after implantation, but was completely resorbed after 3 months. This preliminary study demonstrated that the use of an alginate as a biological sealant instead of proteins such as collagen, gelatin, and albumin may be a feasible approach to developing imprevious textile arterial prostheses, since the proteins have been reported to be generally unstable, hard to obtain in pure forms, not easy to crosslink and control resorption rate, and difficult to render compatible with standard storage and sterilization procedures. © 1997 John Wiley & Sons, Inc. J Biomed Mater Res, 36, 200-208, 1997.
    Additional Material: 5 Ill.
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  • 8
    ISSN: 0021-9304
    Keywords: chargeable functional groups ; gradient surfaces ; corona discharge ; surface grafting ; platelet adhesion ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine , Technology
    Notes: Functional group gradients were prepared on low-density polyethylene (PE) sheets. The surface density of grafted functional groups was gradually changed along the sample length by way of corona discharge treatment with gradually increasing power following graft copolymerization of acrylic acid (AA), sodium p-styrene sulfonate (NaSS), or N,N-dimethyl aminopropyl acrylamide (DMAPAA). AA and NaSS are negatively chargeable and DMAPAA is positively chargeable in phosphate-buffered saline or plasma solution at pH 7.3-7.4. The prepared functional group gradient surfaces were characterized by measurement of the water contact angle, by electron spectroscopy for chemical analysis, and by Fourier transform infrared spectroscopy in the attenuated total reflectance mode. All these measurements indicated that the functional groups were grafted onto the PE surfaces with gradually increasing density. The platelets adhered to the functional group gradient surfaces along the sample length were counted and observed by scanning electron microscopy. It was observed that the platelet adhesion to the gradient surfaces decreased gradually with the increasing surface density of functional groups. This may be related to the hydrophilicity of the surfaces. The DMAPAA-grafted surface showed a large amount of platelet adhesion, probably due to its positive charge character, while the AA-grafted surface, which is charged negatively, showed poor platelet adhesion. However, the NaSS-grafted surface, which is also charged negatively, showed a relatively large amount of platelet adhesion. This may be associated with the existence of an aromatic ring close to the ionizable group in NaSS. It seems that surface functional groups and their charge character, as well as wettability, play important roles for platelet adhesion. © 1998 John Wiley & Sons, Inc. J Biomed Mater Res, 40, 180-186, 1998
    Additional Material: 10 Ill.
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  • 9
    ISSN: 0935-6304
    Keywords: Capillary GC ; Enantiomer resolution ; Chiral stationary phase ; Derivated cyclodextrins ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Three new β-cyclodextrin derivatives, heptakis(6-O-isopropyldi-methylsilyl-2,3-di-O-ethyl)-β-cyclodextrin, heptakis(6-O-thexyldi-methylsilyl-2,3-di-O-ethyl)-β-cyclodextrin, and heptakis(6-O-cy-clohexyldimethyl-2,3-di-O-ethyl)-β-cyclodextrin (IPDE-β-CD, TXDE-β-CD, and CHDE-β-CD), were synthesized and the enan-tioselectivities of these three CD derivatives and heptakis(6-O-tert-butyldimethylsilyl-2,3-di-O-ethyl)-β-cyclodextrin (TBDE-β-CD) were compared for GC separation of a range of chiral test com-pounds. In particular TXDE-β-CD showed much higher enentio-selectivity than TBDE-β-CD. Enentioselectivities of IPDE-β-CD and CHDE-β-CD are somewhat lower than that of TXDE-β-CD and CHDE-β-Cd are somewhat lower than that of TXDE-β-CD. These observations are indicative of significant effects of subtle changes in the structure of the 6-O-substituent on the enantioselec-tivity of the β-CD derivatives. The difference in enantioselectivities of the 6-O-substituted CD derivatives were explained in terms of relative contributions of the effects of hydrophobicity and steric hindrance of the substituent to the inclusion process. CHDE-β-CD showed the lowest enantioselectivity among the threederivatives. It is likely that the unfavorable steric hindrance of the bulky cyclo-hexyl group plays a greater role than the favorable hydrophobicity effect of the cyclohexyl group in the inclusion process in CHDE-β-CD. IPDE-β-CD showed lower selectivity than TXDE-β-CD and TBDE-β-CD. In the case of these CD derivatives having acyclic substituents the relative hydrophobicity of the substituent seems to be a dominant factor affecting the inclusion process. Isopropyl groups factor affecting the inclusion process. Isopropyl groups are less hydrophobic than thexyl and tert-butyl groups.
    Additional Material: 4 Ill.
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  • 10
    ISSN: 0887-624X
    Keywords: poly(arylene sulfide)s ; poly(phenylene sulfide)s ; copolymer composition ; thermal properties ; molecular weight ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Copoly(p-phenylene/biphenylene sulfide)s, PPBS were prepared from sodium sulfide trihydate(Na2S·3H2O), p-dichlorobenzene (DCB), and 4,4′-dibromobiphenyl (DBB) comonomers in N-methyl-2-pyrrolidinone (NMP) solvent using an autoclave. The molecular weights of PPBS copolymers were determined by high temperature (210°C) GPC in 1-chloronaphthalene solvent. The reaction temperature had little effect on the molecular weights of PPBS copolymers with water as additive at the level of 3 mol H2O per 1 mol Na2S. PPBS copolymer, however, showed maximum molecular weight of Mw = 24.1 × 103 with the total water content of 9 mol H2O per 1 mol Na2S at an optimum polymerization temperature of 270°C. The resulting PPBS copolymer sample showed higher Tg (by 30°C) and lower Tm (by 10°C) than PPS homopolymer prepared under similar conditions. © 1996 John Wiley & Sons, Inc.
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