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  • 2020-2022
  • 1980-1984  (7)
  • 1960-1964  (13)
  • 1890-1899
  • Alkenes
  • Fibers
  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 22 (1983), S. 440-455 
    ISSN: 0570-0833
    Keywords: Initiation ; Addition ; Polymerization ; Alkenes ; C-C coupling ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Spontaneous addition and polymerization reactions of alkenes of different electron-densities result in a wide variety of small organic molecules and high polymers. Tetramethylenes are proposed as key intermediates, i.e. resonance hybrids of 1,4-diradical and zwitterionic limiting structures. Their character is determined by the substituents at the terminals: Zwitterionic character is favored by strong donors, such as alkoxy and dialkylamino groups, at the carbenium center and strong acceptor group such as diesters and cyano-esters, at the acceptor end, and aryl and vinyl groups as donors. Zwitterionic tetramethylenes initiate ionic homopolymerization, while diradical tetramethylenes initiate alternating copolymerization, thus providing an extremely sensitive technique for the detection and characterization of these intermediates. The effects of the donor and acceptor substituents can be arranged as an “Organic Chemist's Periodic Table”, wherein the areas of mechanistic change clearly emerge and which provides predictive capability. - This unifying concept of bondforming initiation is extended to spontaneous addition and polymerization reactions of heteroatom acceptor molecules and 7,7,8,8-tetrasubstituted quinodimethanes and of compounds possessing labile σ-bonds, such as halogens and peroxides. Radical-ion pairs, charge-transfer complexes and adventitious impurities are excluded as significant initiators.
    Additional Material: 1 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 22 (1983), S. 753-764 
    ISSN: 0570-0833
    Keywords: Addition ; Free radicals ; Alkenes ; C-C coupling ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: There are many reactions in which CC bonds are formed by addition of free radicals to alkenes. Information about the mechanism is important for the synthesis of specific target molecules. The rate of addition of alkyl radicals to alkenes is controlled by steric and polar effects. The stabilities of the educts and products are of only limited importance, since the transition states for these exothermic reactions occur very early on the reaction coordinate. Variations in reactivity and selectivity can be described using frontier orbital theory: for nucleophilic radicals the dominant interactions are those between SOMO's and LUMO's, and for electrophilic radicals those between SOMO's and HOMO's. The large differences in the steric effects of α - and β- substituents of alkenes can be explained by postulating an unsymmetrical transition state -  the radical approaches one of the C atoms preferentially. Regioand stereoselectivities can be predicted and are determined, in general, by steric effects.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1612-1112
    Keywords: Alkenes ; Gas-solid chromatography ; Ion exchangers ; Alkene separation ; Selectivity ; Specific interactions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The gas chromatographic selectivity of K+, Zn2+, Ag+, Ni2+, and Cd2+ forms of a cation exchange packing have been determined for a set of 44 C2 to C8 alkenes. The retention characteristics of each ion are broken down into electronic (charge-transfer) and steric effects associated with the alkene sub-populations of each carbon number. Almost every pair of alkenes tested can be separated on at least one of these packings. Retention is much stronger on the ion exchangers than on metal-ion containing packings in gas-liquid chromatography, even with shorter columns and higher temperatures.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 1432-2048
    Keywords: Cellulose synthetase ; β-1,3-Glucan synthetase ; Fibers ; Gossypium ; Membrane potential ; Polysaccharide synthesis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Conditions which induce a transmembrane electrical potential, positive with respect to the inside of membrane vesicles, result in a substantial (4–12-fold) stimulation of the activity of membrane-associated β-glucan synthetases in a membrane preparation derived from the developing cotton (Gossypium hirsutum L.) fiber. Induction of electrical potentials which are negative with respect to the inside of the membrane vesicle results in little or no stimulation of β-glucan synthesis. Those products whose synthesis is stimulated are mainly β-1,3-glucan, but there is also a considerable increase in β-1,4-glucan. No α-1,4-glucan (starch) was detected in the reaction products. A transmembrane pH gradient was found to have no effect on β-glucan synthesis. The results indicate that a transmembrane electrical potential can influence, either directly or indirectly, the activity of membrane-associated polysaccharide synthetases.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 0570-0833
    Keywords: Analytical methods ; Fibers ; Oligomers ; Polymers ; Synthetic fibers ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Oligomers belong to the gray area between low molecular weight chemistry and macromolecular chemistry. Although they represent an undesirable “natural impurity” in fiber-forming polycondensates, they serve as useful model compounds for the corresponding polymers in fundamental research. Whereas for many years new classes of oligomers were being made preparatively accessible and the isolation of higher oligomers in pure form was being pursued, at the present time the emphasis is on analysis. By a combination of classical chemical and instrumental methods of analysis from polymer and organic chemistry, the identification of oligomers of unknown structure, the analytical control of their synthesis and the determination of their content in technical polymers has meanwhile become a routine task.
    Additional Material: 6 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Planta 148 (1980), S. 305-311 
    ISSN: 1432-2048
    Keywords: Bacitracin ; Cellulose (synthesis inhibitors) ; Coumarin ; 2,6-Dichlorobenzonitrile ; Fibers ; Gossypium
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Several compounds were tested for their ability to inhibit the in-vivo synthesis of cellulose and other cell-wall polysaccharides in fibers of cotton (Gossypium hirsutum L.) developing on in-vitro cultured ovules. Inhibitory effects were measured by the ability of the compounds to inhibit the incorporation of radioactivity from [U-14C]glucose into these cell-wall polymers. Of the compounds surveyed, 2,6-dichlorobenzonitrile (DCB) was the most effective and specific one for its effects on cellulose synthesis when compared to its effect on the synthesis of other cell-wall components. At 10 μM DCB caused 80% inhibition of cellulose synthesis, and the effect was reversed upon removal of the DCB, with recovery to 90% of the control rate. Two analogs of DCB, 2-chloro-6-fluorobenzonitrile and 2,6-dichlorobenzene carbothiamide, were as specific and nearly as effective as DCB with respect to their effects on cellulose synthesis. Coumarin, generally regarded as an inhibitor of cellulose synthesis in other plant systems, was effective in cotton fibers in millimolar concentrations and, like DCB, was relatively specific with regard to its effect on cellulose synthesis. DCB and coumarin inhibited the synthesis of both primary and secondary wall cellulose. Bacitracin, an inhibitor of the cycling of phosphorylated polyprenols involved in cell-wall synthesis in bacteria, and ethylenediaminetetracetic acid (EDTA) and ethyleneglycol-bis-(β-amino-ethylether)-N,N′-tetracetic acid (EGTA), chelators of civalent cations, were also effective, although only at relatively high concentrations, in inhibiting incorporation of radioactivity into cellulose.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 1573-1561
    Keywords: Alkenes ; mercuration-demercuration ; methoxyethers ; mass spectrometry ; insect hydrocarbons ; honeybee
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract The positions of double bonds in olefins can be readily determined by a sodium borohydride reduction of their methoxymercuration products followed by mass spectrometry. Fragmentation of the methoxy derivative in the mass spectrometer results in cleavage on either side of the methoxy group to give intense fragment ions which are characteristic of each isomer. This simple and convenient microanalytical technique was applied to several synthetic standards and insect derived olefins, including the alkenes from the cuticular lipids of the honeybeeApis mellifera L.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 3 (1964), S. 245-249 
    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.
    Additional Material: 2 Tab.
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 3 (1964), S. 460-470 
    ISSN: 0570-0833
    Keywords: Heat resistance ; Fibers ; Polymers ; Materials science ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This survey is principally concerned with papers published since 1959 on hydrocarbon polymers, aliphatic poly(terephthalamide) fibers, poly(hydroxybenzoic acid) films, poly(oxadiazole) fibers, poly(benzimidazole) films, poly(phenyltriazole) films, poly(pyromellitimide) films, and fibers from cyclized poly(acrylonitrile). All these materials have extremely high melting points and satisfactory in-use characteristics at high temperatures.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 10
    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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  • 11
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 2 (1963), S. 295-308 
    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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  • 12
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 2 (1963), S. 704-714 
    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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  • 13
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 2 (1963), S. 410-420 
    ISSN: 0570-0833
    Keywords: Oligomers ; Pleionomers ; Polymers ; Fibers ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The term “oligomer” is defined, and a survey of methods for the isolation and synthesis of cyclic and linear oligoesters, oligourethanes, oligo(acrylonitriles), and oligoamides is presented. The oligomers serve a valuable function as model substances for the investigation of many properties of the corresponding high polymers. This is shown using several examples (infrared spectroscopy, X-ray spectroscopy, viscosity).
    Additional Material: 1 Ill.
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  • 14
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 1 (1962), S. 80-88 
    ISSN: 0570-0833
    Keywords: Oxidation ; Palladium ; Catalysis ; Alkenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oxidation of olefins to carbonyl compounds with palladium compounds, especially the oxidation of ethylene to acetaldehyde, is at present carried out on a technical scale. The reaction takes place via a palladium-olefin complex, the formation of which is inhibited by halide ions. Hydrolysis to the carbonyl compound is inhibited by hydrogen ions. The knowledge gained by studying the reaction of olefins with pure solutions of palladium salts allows important conclusions to be drawn concerning the action of technical catalyst solutions containing copper and palladium chloride.
    Additional Material: 9 Ill.
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  • 15
    ISSN: 0570-0833
    Keywords: Pyrrolidone ; Polyamides ; Fibers ; Lactams ; Polymerization ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The industrial production of capryllactam (1-azacyclononan-2-one) and of laurolactam (1-azacyclotridecan-2-one) starts with cyclization of acetylene or butadeine to give cyclooctatetraene or cyclooctadiene, or cyclization of butadiene to give cyclododecatriene. Further steps are: oxidation of the cyclic hydrocarbon to the ketone, formation of the oxime, and rearrangement of the latter with sulfuric acid. Pyrrolidone can be prepared from acetylene and formaldehyde by way of butyrolactone. The behavior of the lactams during polycondensation is described and the properties of the resulting fibers are compared with those of the known polyamide fibers.
    Additional Material: 2 Ill.
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  • 16
    ISSN: 0570-0833
    Keywords: Lactams ; Polymerization ; Fibers ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: β-Lactams can be prepared by cyclization of β-aimno acid esters. Recently they have become available also from olefins by addition of N-carbonysulfamyl chloride (isocyanatosulfonyl chloride) and from aldehydes by reaction with N-carbonylsulfamyl chloride and ketene. Condensative or anionic polymerization results in polyamides the chains of which contain many more amide groups than the chains of polyamides of the nylon-6 type. Hence the new polymers resemble silk moreclosely. Fibers and films can be prepared from solution.
    Additional Material: 7 Ill.
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  • 17
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 1 (1962), S. 532-537 
    ISSN: 0570-0833
    Keywords: Polyacrylonitrile ; Fibers ; Azatrimethinecyanines ; Dyes/Pigments ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Like all basic dyes, azatrimethinecyanines possess a good dyeing affinity for acrylic fibers. Compounds with isolated nitrogen atoms in the trimethine chain show insufficient light fastness, whereas good to excellent fastness to light is displayed by compounds having neighboring nitrogen atoms in the chain. Thus, a working hypothesis stating that the light fastness of trimethinecyanines on acrylic fibers is improved by progressive replacement of methine groups by nitrogen atoms has been partially confirmed.
    Additional Material: 3 Tab.
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  • 18
    ISSN: 0570-0833
    Keywords: Elastomers ; Fibers ; Polyurethanes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Highly elastic polyurethanes suitable for fiber production can be obtained by various synthetic routes based on diisocyanate polyaddition processes. Macrodiisocyanates obtained from long chain diols and diisocyanates are allowed to react with polyamines during fiber formation (chemical spinning process) or the macrodiisocyanates are treated in solvents (e.g. dimethylformamide) with polyamines to give highly viscous, spinnable solutions of polymer. Both methods yield highly elastic polymers with wide-mesh network structures. The production of polyurethane fibers and their structures and physical properties are described.
    Additional Material: 6 Ill.
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  • 19
    ISSN: 0570-0833
    Keywords: Copolymers ; Fibers ; Vinylidenedicarbonitrile ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Vinyldendicarbonitrile (Vinylidene cyanide) on free redical catalyzed copolymerization shows a much stronger tendency to form 1:1 alternating copolymers than acrylonitrile. While bulk poly(vinylidene cyanide) fails to crystallize, despite its molecular symmetry, several alternating copolymers are readily crystallizable, notably those containing butadiene, isoprene, isobutylene, or vinylidene chloride. Fibers have been prepared from a number of the higher melting copolymers and examined for physical properties. Fibers from the vinyl acetate and vinyl chloride copolymers show expectional elastic behavior both when dry and wet. The fiber from the vinylidene cyanide |vinyl acetate alternating copolymer (Darvan® nytril fiber) is only moderately oriented and is characterized by exceptional softness and excellent elastic recovery and resilience, both when dry and wet.
    Additional Material: 9 Ill.
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  • 20
    ISSN: 0570-0833
    Keywords: Long periods ; Polyethylene ; Fibers ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Meridional reflections appearing in small-angle X-ray diffraction diagrams of drawn polyethylene are caused by a nearly periodic arrangement of crystalline and disordered regions. The long period, which is determined by the average distance between two consecutive crystallites, depends on the method of preparing the sample. The time and temperature dependences of the positions of the small-angle reflections have been investigated. The growth of the long period of unoriented bulk polyethlene and polyethylene single crystal follows the same time dependence as that of stretched films. However, characteristic differences were obseved in the relationship between density and long period; they are attributed to the fact that in single crystals and in material crystallized from the melt, the chains are folded at the boundaries of the crystallites, whereas this in not the case in stretched polyethylene.
    Additional Material: 25 Ill.
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