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  • 1
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The propagation kinetics for the copolymerization of 4-methoxystyrene with methyl methacrylate and 4-methoxystyrene with styrene have been investigated using a pulsed laser technique. The dependence of the copolymerization propagation rate constant on the monomer feed ratio shows a diviation from classic Mayo-Lewis model kinetics for 4-methoxystyrene with methyl methacrylate but not for 4-methoxystyrene with styrene. These results have been interpreted to indicate that a penultimate effect is apparent in the first monomer pair but not in the second. With r1r2 = 0.092 for the copolymerization of 4-methoxystyrene with methyl methacrylate and r1r2 = 0.95 for 4-methoxystyrene with styrene, it is suggested that a deviation of the product of the coplymerization reactivity ratios from unity may be an indication of the presence of a penultimate effect.
    Additional Material: 5 Ill.
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  • 2
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of alkylthio-substituted aromatic diamines was synthesized using a convenient high yield procedure. The method consisted of heating a mixture of dialkyl disulfide and aromatic diamine in the presence of cuprous iodide or other Lewis acid catalyst. Dialkyl disulfide was continually replenished as consumed, throughout the reaction, to maintain the desired reaction temperature. Compounds so prepared were isolated by first precipitating the catalyst with solid caustic and then vacuum flashing the crude products. When desired, the final product purity could be increased by washing with acid to remove starting material or reaction intermediates. The final products were often liquids or low melting solids and showed utility as curatives for polyurethane cast elastomers. Alkylthio substitution of the aromatic diamines lowered reactivity toward isocyanates and generally provided for facile processing during molding. The series of derivatives allowed for great flexibility in controlling both diamine reactivity and the physical properties of the final elastomers. These benefits arose from the diverse electronic, steric and isomeric properties of the derivatives. Polymers were prepared from the alkylthio-substituted compounds and commercially available TDI-based prepolymers using conventional cast elastomer techniques. The physical properties of the polymers were determined and their relation to alkylthiodiamine structure examined.
    Additional Material: 7 Ill.
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  • 3
    ISSN: 0887-624X
    Keywords: phenyl ethynyl ether imides ; amorphous or semicrystalline morphology ; volatile free thermosetting matrix ; structural adhesives ; composites ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Fully cyclized, organo soluble, phenylethynyl-terminated, ether-imide oligomers of 2-10,000 g/mol (Mn) were prepared by the reaction of 2,2′-bis[4-(3,4-dicarboxyphenoxy)phenyl]-propane dianhydride (bisphenol-A dianhydride, BPADA) with a stoichiometric excess of either para, meta, or isomeric mixtures of phenylene diamine and phenylethynylphthalic anhydride (4-PEPA) endcapper. High para-containing oligomers produced semicrystalline powders, but the all meta isomer was completely amorphous. The lower molecular weight oligomers displayed an attractive low viscosity melt and were cured to very high gel content networks at 350-380°C for 30-90 min. The cured 3000 g/mol oligomers showed a (DSC) glass transition temperature (Tg) of 267°C and produced tough, solvent-resistant films. Excellent adhesion to surface-treated titanium alloys was achieved, as judged by single-lap shear measurements. Resin infusion molding was conducted, which permitted low-void, graphite-fabric composite panels to be prepared. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2943-2954, 1997
    Additional Material: 7 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Polymers for Advanced Technologies 1 (1990), S. 345-349 
    ISSN: 1042-7147
    Keywords: Graft copolymers ; Macromolecular homing devices ; Colloidal drug carriers ; bone marrow targeting ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: A series of novel graft (comb) copolymers composed of a hydrophobic backbone and hydrophilic side chain grafts are described for the in vivo targeting of colloidal carriers. The new copolymers, when coated on nanometer size particles (nanospheres, nanocapsules), substantially reduce the capture of the particles by the reticuloendothelial system (RES) and show potential for targeting to the bone marrow.
    Additional Material: 3 Ill.
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  • 5
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A soluble aromatic poly (amic acid) film was converted to a soluble polyimide by staging at 25°C intervals to 325°C and characterized at each interval by several analytical methods. The behavior observed was consistent with an interpretation that a reduction occurred in molecular weight of the poly (amic acid) during the initial stages of cure before the ultimate molecular weight was achieved as a polyimide. This interpretation was supported by the results of solution viscosity, gel permeation chromatography, low angle laser light scattering photometry, and infrared spectroscopy analyses. The results of this study serve to increase our fundamental understanding of how polyimides are thermally formed from poly (amic acid)s.
    Additional Material: 9 Ill.
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  • 6
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We present results of molecular orbital thory calculations of the interactions of acrylic polymers with aluminum, with a view toward understanding the nature of chemical bonding at the corresponding polymer-metal interfaces. The reported results are for the interactions of polymer model compounds with metal atoms (as opposed to our ongoing studies with metal surfaces). As such, the results relate to experimental studies where small dosages of metal atoms are evaporated onto polymer surfaces in pristine high vacuum environments. Our studies have been conducted within the theoretical framework of Hartree-Fock molecular orbital theory. We find that aluminum atoms interact primarily with the carbonyl group of acrylic polymers. The reaction proceeds by the metal atoms interacting with both the carbon and the oxygen atoms of the carbonyl functionality. This weakens the C=O bond. Finally, the carbonyl bond loses double bond character, and strong AL - O bonds are formed. Our results are compared to experimental data, and the implications of the detailed nature of bonding for adhesion applications are discussed.
    Additional Material: 9 Ill.
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  • 7
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The behavior of catalytic chain transfer in semi-batch emulsion polymerization has been studied for two monomers, viz, methyl and n-butyl methacrylate. Two different catalytic chain transfer reagents were used with different water solubilities: cobaloxime boron fluoride (COBF), which was found to partition approximately equally between organic and aqueous phases, and tetra-phenyl cobaloxime boron fluoride (COPhBF), which was found to reside predominantly in the organic phase. The difference in hydrophilicity between the two transfer agents was found to affect the polymerization mechanism. COBF exhibited superior transfer behavior in all cases, whereas the restricted mobility of the COPhBF had a deleterious effect on the efficiency of the transfer mechanism. The best results were achieved under monomer flooded conditions using COBF. MALDI-TOF mass spectrometry analysis shows catalytic chain transfer to be the dominant mechanism initiating and stopping chain growth as none of the chains appear to have initiator fragment end groups. Analysis of copolymers by MALDI-TOF mass spectrometry reveals both molecular weight and composition data. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 859-878, 1997
    Additional Material: 21 Ill.
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  • 8
    ISSN: 0887-6258
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    ISSN: 0887-6258
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 10
    ISSN: 0887-624X
    Keywords: styrene ; methyl methacrylate ; pulsed-laser polymerization ; “living” free radical ; propagation rate coefficient ; solvent effects ; benzyl alcohol ; N-methyl pyrrolidinone ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The free radical propagation rate coefficients of both Methyl Methacrylate (MMA) and Styrene (STY) have been measured using Pulsed-Laser Polymerization. The effect of solvents on the propagation rate coefficient, kp, is reported for several solvents, namely, bromobenzene, chlorobenzene, dimethyl sulphoxide, diethyl malonate, diethyl phthalate, benzonitrile, and benzyl alcohol, at 26.5°C. This preliminary data indicated that benzyl alcohol (BzA) had a large effect on the MMA propagation reaction. As earlier work indicated that N-methyl pyrrolidinone (NMP) would also have a large effect on the kp of MMA, Arrhenius parameters were evaluated for both MMA and STY at two different concentrations of monomer in BzA and NMP. BzA had a significant effect (at 95% confidence) increasing both the activation energy (Ea) and the preexponential factor (A) for MMA and STY. In NMP, a similar trend is observed for MMA polymerization; however, while a solvent effect on STY was observed, the effect on Ea and A was too small to discern with confidence. A series of additional experiments was performed to evaluate the influence of camphorsulfonic acid (CSA) as an additive in STY polymerization. There was no effect of CSA on kp, confirming that the strong effect CSA has on “living” radical polymerization of styrene does not originate from complexation leading to an accelerated propagation step but rather by altering the ratio of active-to-dormant chains in the reaction. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2311-2321, 1997
    Additional Material: 12 Ill.
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