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  • Polymers  (12)
  • Alkenes  (6)
  • Wiley-Blackwell  (18)
  • 1990-1994  (10)
  • 1960-1964  (8)
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  • Wiley-Blackwell  (18)
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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    ISSN: 0570-0833
    Keywords: Polymers ; High-temperature polymers ; Materials science ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Research on high-temperature organic polymers was initiated in the late 1950s primarily to meet the needs of the aerospace and electronics industry. Since then, many different heat-resistant polymer systems have been reported, of which several are now commercially available. These polymers are used in many diverse applications such as circuitry in microelectronic components, coatings on cookware, binders in brake systems, sealants for fuel tanks in high-speed aircraft, gears in copying machines, structural components in high-speed aircraft, and space vehicles, films and wire coatings for electrical insulation. Worldwide use for high-temperature polymers in 1988 was estimated at 90 million kilograms with a value of $ 2.3 billion. This market is expected to double by the end of this decade. The major polymer classes discussed in the present paper are polyimides and poly(aryl ethers).
    Additional Material: 1 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    ISSN: 0570-0833
    Keywords: Polymers ; Liquid crystals ; Crystalline polymers ; Materials science ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: During the past ten years there has been a sharp increase in interest in the opportunities afforded by R & D in the field of specialty polymers. Interest is mainly being shown in two distinct categories of polymers, namely, (a) polymers which are used in very small quantities to fulfill critical needs as a part of device system, and (b) high-performance engineering polymers which significantly extend their mechanical and thermal properties for structural applications. The first category ranges from advanced resists and insulating layers for microelectronic devices to membranes for filtration systems. The second category encompasses improved matrices for advanced composites as well as liquid crystalline polymers. In the present paper an overview is first given of the emerging opportunities for advanced materials and particularly specialty polymers. The status of work on liquid crystalline copolyesters is then discussed with special emphasis on one of the major problems confronting this field, namely interpreting the microstructure of the copolyesters.
    Additional Material: 5 Ill.
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  • 3
    ISSN: 0570-0833
    Keywords: Kinetics ; Addition ; Alkenes ; Reaction mechanisms ; Carbocations ; C-C coupling ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The addition of carbenium ions to CC double bonds, a key step in many syntheses in organic and macromolecular chemistry, is analyzed using the Lewis acid promoted reactions of alkyl chlorides with alkenes as an example. Stereochemical and kinetic experiments suggest that the transition state is slightly bridged and product-like. Rearrangements of the carbenium ions that result from the electrophilic attack can be minimized by adding salts with nucleophilic counter ions. The thermodynamics of the addition reactions are analyzed, and the conditions necessary in order to observe the back reaction (i.e. the Grob fragmentation) are discussed. Multiparameter equations that predict rate constants are derived from kinetic studies on the reactivities of carbenium ions and alkenes. Reactivity-selectivity relationships over a reactivity range that covers eight orders of magnitude show that the structure of the transition state is only changed by variation of substituents in the immediate vicinity of the reaction center.
    Additional Material: 8 Ill.
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  • 4
    ISSN: 0570-0833
    Keywords: Materials science ; Polymers ; Polycarbonates ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polycarbonate together with the acrylonitrile/butadiene/styrene copolymers, and the poly amides constitute the leading groups of engineering thermoplastics; for polycarbonate in particular, continued dynamic growth is prophesized.The underlying reason for this lies not only in its outstanding combination of technical properties and excellent price/performance balance, but also in the chemical and physical potential inherent in the basic structure of polycarbonate. The following review demonstrates with examples how this potential can be used in the development of new polycarbonates through the incorporation of alternative monomers, changes in the linear structure, end group variation, addition of special additives, and blending. The main emphasis of this articles lies in the development of polycarbonates resistant to high temperature, with a good balance of technologically valuable properties. For scientific and practical interests a new criterion is offered for polycarbonates having both high-temperature stability and impact strength.“One must not only make a discovery, but also realize that a discovery has been made.”Hermann Schnell [1]
    Additional Material: 9 Ill.
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  • 5
    ISSN: 0570-0833
    Keywords: Soft matter ; Nobel lecture ; Fluids ; Polymers ; Surfactants ; Liquid crystals ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 6
    ISSN: 0570-0833
    Keywords: Emulsion polymerization ; Polymerization ; Polymerization ; Alkenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ionizing radiation induces the polymerization of some vinyl monomers in aqueous emulsion with high radiation yields. With identical emulsion compositions, the kinetics of this reaction and the kinetics of emulsion polymerization induced by water-soluble initiators are very similar. The rate of reaction in emulsion polymerization is about one hundred times greater than in bulk polymerization. The initiation of emulsion polymerization by means of ionizing radiation permits uniform “illumination” of the reacting volume, as well as almost any desired variation in the frequency of initiation during the reaction. The sharp decrease in the overall rate of reaction when initiation is interrupted during emulsion polymerization of styrene induced by γ-rays contradicts the earlier concept of sharply separated reaction zones.
    Additional Material: 11 Ill.
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  • 7
    ISSN: 0570-0833
    Keywords: Titanium ; Alkenes ; Polymerization ; Titanium ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: At low temperatures, ethylene and α-olefins (Δ1-olefins or 1-alkenes) are rapidly converted into oligomrs by the two-component organometallic catalyst CH3TiCl3·CH3AlCl2. To achieve smooth oligomerizations, aromatic or chlorinated hydrocarbons must be used as solvents. Although the activity of the titanium-carbon bond is enhanced by the aluminum component of the catalyst, the aluminum and its methyl group do not participate in the reaction proper; the latter proceeds exclusively at the titanium-carbon bond. The reaction will olefins can be used as an analytical method for the quantitative determination of the titanium-carbon bond in admixture with the organoaluminum component. It is thus possible to follow the reaction leading to formation of the catalyst from titanium tertrachloride, as well as the processes occurring at the titanium-carbon bond during the oligomerization of olefins. All the observations indicate that the catalyst possesses an ionic structure which is determined by the solvent. It is shown that the initial reaction step probably involves formation of a complex between the olefin and the alkyltitanium cation. The reaction scheme proposed is based on organometallic reactions which are characterized by carbanion and hydride transfers within the olefin-cation complex. This mechanism, which is unusual for Ziegler catalysts, is due to the predominance of hydride transfers.
    Additional Material: 2 Ill.
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  • 8
    ISSN: 0570-0833
    Keywords: Koch carboxylic acid synthesis ; Carboxylic acids ; Alkenes ; Isomerization ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: When straight-chain mono-olefins, from pentene to decene, are subjected to the Koch carboxylic acid synthesis by the addition of CO and H2O or CH3OH in the presence of strongly acidic catalysts, not only the expected secondary acids, but also mixtures of a specific type of tertiary acids or their methyl esters are formed. When the catalysts contain boron trifluoride, the secondary acids are formed in ratios of isomers which are, within the scope of this investigation, independent of the experimental conditions and which agree well with the values calculated from the isomer equilibria of the corresponding n-olefins. Using concentrated sulfuric acid as catalyst, a larger proportion of tertiary acids is obtained than with BF3-catalysis, and amongst the secondary acids, those isomers predominate in which the COOH group is situated near the centre of the molecule.
    Additional Material: 1 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    ISSN: 0570-0833
    Keywords: Copolymers ; Polymers ; Solid-phase synthesis ; Proteins ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chemical total synthesis of proteins using solid supports has made great progress. It is therefore becoming a reality what E. Fischer already predicted in 1902Cited from Nobel Lectures - Chemistry 1901-1921, Elsevier, Amsterdam 1966, p. 34.: “I foresee the time when physiological chemistry… is able to prepare synthetic enzymes.” The synthesis of peptides of up to 20 amino acids by the well-established solid-phase procedure on polymeric supports (SPPS) has made great progress through the development of newer supports. At the same time, methods have emerged which facilitate the separation and characterization of peptides, thus allowing optimization of the synthesis of pure materials. The new supports which enable one to synthesize peptides by a rapid continuous flow procedure are characterized by hydrophilicity, beads of approximately equal size, similar swelling properties in the solvents used for peptide synthesis, and stability at high pressure. With graft copolymers of weakly cross-linked polystyrene and linear polyethylene glycol (PEG), the synthetic cycle for coupling of one amino acid can routinely be reduced to 10-20 min with a concomitant higher yield. With beads of monodispersed graft copolymer of 10 μm diameter, a synthetic cycle can, in principle, be shortened to 1-5 min. By utilizing this high-speed solid-phase procedure, larger peptides up to the size of proteins could also be prepared in a few hours. With newer mass spectroscopic methods such as ion-spray mass spectrometry, peptides of up to a molecular mass of 100 kDa can be characterized, and with the advent of capillary electrophoresis, another very efficient separation tool, besides HPLC, is at our disposal.
    Additional Material: 27 Ill.
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  • 10
    ISSN: 0570-0833
    Keywords: Addition ; Alkenes ; Electrophilic reactions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Various structures have been proposed for the intermediates of electrophilic additions onto olefins; these include halonium ions, classical carbonium ions, π-complexes (i.e. nonclassical carbonium ions), and π-complexes with back-coordination. It is shown here that it is impossible to use any one of these entities alone to explain all such electrophilic additions; the electrophile itself determines the nature of the transition state formed. Polar addition of hydrogen halides onto olefins appears to proceed via a classical carbonium ion which does not occur as the free ion but as an undissociated ion pair. Various other mechanisms have been excluded by studies reported here of the stereochemical course of such additions.
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