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  • 1
    Electronic Resource
    Electronic Resource
    Studies on polymerizations initiated by syncatalytic systems based on aluminium organic compounds, 6Part 5: cf.6.. Comparison with isobutene polymerizations initiated by ethylaluminium dichloride or aluminium trichloride (1977)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 178 (1977), S. 2223-2234 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The results of previous studies carried out on the polymerization of isobutene initiated by diethylaluminium halides plus halogens are compared with results obtained with other syncatalytic systems such as diethylaluminium chloride (or triethylaluminium) plus hydrochloric acid (or tert-butyl chloride), as well as with results obtained with aluminium compounds such as ethylaluminium dichloride or aluminium trichloride which do not require co-initiators to initiate the polymerization of isobutene. The kinetic data indicate clearly that the polymerization of isobutene initiated by syncatalytic systems is characterized by a relatively slow initiation and by the absence of important termination reactions and of transfer with monomer. In contrast to this, the polymerizations initiated by strong Lewis acids such as ethylaluminium dichloride or aluminium trichloride show a much faster initiation and stop at incomplete conversion which indicates that at least one efficient termination reaction is operative. It is also demonstrated that this termination reaction produces at least one substance which acts as a co-initiator for the isobutene polymerization initiated by diethylaluminium halides or triethylaluminium.
    Additional Material: 16 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1977.021780809
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  • 2
    Electronic Resource
    Electronic Resource
    Studies on polymerizations initiated by syncatalytic systems based on aluminium organic compounds, 4Part 3: cf. 7.. Polymerization of isobutene initiated by diethylaluminium chloride and chlorine (1975)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 176 (1975), S. 2319-2337 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die durch Diäthylaluminiumchlorid + Chlor ausgelöste Polymerisation des Isobutens wurde untersucht, um den Einfluß der Konzentration der verschiedenen Reagenzien, der Temperatur und des Lösungsmittels auf die Polymerisationsgeschwindigkeit und das Molekulargewicht zu bestimmen. Kinetische Studien in Methylchlorid bei -45°C mit einer Isobutenkonzentration von 0,1 mol/1 haben gezeigt, daß die Initiierung relativ langsam verläuft, wodurch die Umsatzkurve S-förmig gestaltet wird. Die Polymerisationen von einer zweiten und von weiteren Zugaben von Isobuten verlaufen ohne Beschleunigung und viel schneller als die erste Polymerisation. Dies zeigt, daß Abbruchreaktionen unbedeutend sind.Der Polymerisationsgrad wird hauptsächlich durch Übertragungsreaktionen mit Verbindungen bestimmt, deren Konzentrationen denen der Komponenten des synkatalytischen Systems proportional sind. Ein sehr ungewöhnliches Merkmal dieses Systems ist es, daß eine Übertragungsreaktion mit dem Monomer nicht vorliegt.
    Notes: The polymerization of isobutene, initiated by diethylaluminium chloride + chlorine, was studied with the main goal of clarifying the influence of the concentration of the different reagents, the temperature, and the nature of the solvent on the rate of polymerization and on the molecular weight of the products. A kinetic study carried out in methyl chloride at -45°C and with a monomer concentration of 0,1 mol/l, has shown that the polymerization is characterized by a relatively slow initiation which gives the conversion curves an S-shape. Experiments with successive monomer additions showed that the polymerization of the second and subsequent portions of monomer occurs without acceleration and with a much higher rate. This shows that termination reactions are almost negligible.The degree of polymerization depends mainly on the transfer reactions with substances having concentrations proportional to those of the components of the syncatalytic system; transfer with monomer is absent, which is a very unusual feature.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1975.021760812
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  • 3
    Electronic Resource
    Electronic Resource
    Studies on polymerizations initiated by syncatalytic systems based on aluminium organic compounds, 5Part 4: cf.3. Copolymerization of isobutene and isoprene catalyzed by diethylaluminium chloride and chlorine (1975)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 176 (1975), S. 2339-2358 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die wichtigsten Parameter, die die Copolymerisation von Isobuten mit Isopren bei der Initiierung durch das katalytische System Diäthylaluminiumchlorid + Chlor in Methylchlorid steuern werden untersucht, sowie der Einfluß der Konzentration der Katalysatorbestandteile, der Monomeren, des 1-Butens und der Polymerisationstemperatur auf die Ausbeute, das Molekulargewicht und die Zusammensetzung des Copolymeren. Der Copolymerisationsparameter von Isobuten, bezogen auf Isopren, bei -35°C beträgt 2,5 ± 0,5. Die Aktivierungsenergie EM beträgt -23,9 ± 3 kJ/mol und -18,0 ± 2 kJ/mol (-5,7 ± 0,7 und -4,3 ± 0,5 kcal/mol) für das Copolymere mit einem Molenbruch von 0,013 bzw. 0,019 an Isopren, und -24,3 ± 2 kJ/mol(-5,8 ± 0,4 kcal/mol) fur Polyisobutylen. Die Ergebnisse werden mit ahnlichen Angaben für die Systeme Diäthylaluminiumchlorid + tert-Butylchlorid sowie Diäthylaluminiumchlorid + Chlorwasserstoff verglichen. Der Einfluß von Wasser auf die Katalysatoraktivität wird kurz untersucht und erörtert. Außerdem werden einige technologische Daten über typische Copolymere berichtet.
    Notes: An extensive investigation of the main parameters regulating the copolymerization of isobutene and isoprene, initiated by the catalyst system diethylaluminium chloride + chlorine in methyl chloride, was carried out. The influence of the concentration of the catalyst components, of the monomers, of 1-butene, and of the polymerization temperature on the yield, the molecular weight and the composition of the copolymer was studied. The reactivity ratio of isobutene with respect to isoprene is 2,5 ± 0,5 at -35°C. The activation energy M is -23,9 ± 3 kJ/mol and -18,0 ± 2 kJ/mol (-5,7 ± 0.7 and -4,3 ± 0,5 kcal/mol) for the copolymer with a mole fraction of 0,013 and 0,019, respectively, of isoprene, and -24,3 ± 2 kJ/mol (-5,8 ± 0,4 kcal/mol) for polyisobutylene. The results are compared with similar data obtained for the system diethylaluminium chloride + tert-butyl chloride and diethylaluminium chloride + hydrogen chloride. The influence of water on the activity of the catalyst was investigated briefly and discussed. Some technological data obtained with typical copolymers are also reported.
    Additional Material: 16 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1975.021760813
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  • 4
    Electronic Resource
    Electronic Resource
    Studies on polymerizations initiated by syncatalytic systems based on aluminium organic compounds, 7Part 6: cf.6.. Reaction mechanisms (1977)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 178 (1977), S. 2235-2248 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The polymerizations of isobutene and its copolymerizations with isoprene by syncatalytic systems consisting of an aluminium compound R2AlX (with R = alkyl and X = alkyl or halogen) and of a halogen or an interhalogen compound are initiated by the addition of a positive halogen ion to the monomer. Chlorine is the best co-initiator. Whereas in this syncatalyzed polymerization of isobutene the initiation is relatively slow and monomer transfer and termination are unimportant, in the polymerization of isobutene by AlCl3 or EtAlCl2 the initiation is very fast and there is at least one efficient termination. Our interpretation of these results includes a discussion of the different initiations and chain-breaking reactions.In the syncatalyzed polymerizations the initiation rate is governed by the relatively slow interaction of initiator and co-initiator. Since the termination reactions are relatively unimportant, second and subsequent portions of monomer polymerize completely and faster than the first. The polymerizations initiated by AlCl3 or EtAlCl2 stop at incomplete conversion because of a termination which is chlorination of the carbenium ions by the anions; the AlCl3 thus formed is complexed by the unreacted monomer.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1977.021780810
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  • 5
    Electronic Resource
    Electronic Resource
    Electric field effects and electroinitiation in cationic polymerizations (1974)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 175 (1974), S. 1157-1180 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Ergebnisse verschiedener Autoren beim Studium kationischer Polymerisationen in Gegenwart eines starken elektrischen Feldes - wir schlagen dafür den Namen ”elektrobeeinflußte Polymerisationen“ vor - werden kurz zusammengefaßt.Es werden die wichtigsten in den Laboratorien des Autors gefundenen Ergebnisse der ”elektro-beeinflußten“ kationischen Polymerisation von Anethol, Isobutylvinyläther und Cyclohexylvinyläther im konstanten oder im periodisch umgepolten Feld dargestellt. Die Analogien zwischen diesen Ergebnissen und jenen, die aus Untersuchungen elektroinitiierter kationischer Polymerisationen verschiedener Vinylmonomerer mit Tetraalkylammoniumperchloraten, Tetraalkylammoniumjodiden oder Tetraalkylammoniumtrijodiden erhalten werden, werden hervorgehoben.Auf der Basis dieser Analogien erklärt sich die Zunahme der Polymerisationsgeschwindigkeit, die in einigen Fällen beobachtet wird, wenn ein elektrisches Gleichstrom-Feld auf ein zur kationischen Polymerisation fahiges System angewendet wird, als Folge von Prozessen an den Elektroden, und zwar der anodischen Erzeugung von neuen aktiven Zentren durch Elektrolyse der Gegenionen. Diese neue Interpretation kann mit einem mathematischen Modell erfaßt werden, das fur die meisten experimentellen Ergebnisse zutrifft, die bisher bei elektro-beeinflußten und durch Jod initiierten kationi-schen Polymerisationen erhalten wurden.
    Notes: The results obtained by various authors in the study of cationic polymerizations carried out in the presence of an electric field of high strength, that we propose to call “electro-influenced polymerizations”, are shortly reviewed.The most relevant results obtained in the author's laboratories, for the “electroinfluenced” cationic polymerization of anethole, isobutyl vinyl ether and cyclohexyl vinyl ether with constant or periodically reversed field polarity are illustrated.The analogies between these results and those obtained from studies on electroinitiated cationic polymerizations of various vinyl monomers with tetraalkylammonium perchlorates, tetraalkylammonium iodides or tetraalkylammonium triiodides are emphasized.On the basis of these analogies, we interpret the increase of the polymerization rate which is observed in some cases when a d.c. field is applied to a cationically polymerizing system as being due to electrodic processes, namely the anodic generation of new active centres through electrolysis of the counterions. This new interpretation can be formalized in a mathematical model which fits most of the experimental results so far obtained for electro-influenced cationic polymerizations initiated by iodine.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1974.021750408
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  • 6
    Electronic Resource
    Electronic Resource
    Studies on polymerizations initiated by syncatalytic systems based on aluminium organic compounds, 1. Introduction, experimental methods and preliminary results (1975)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 176 (1975), S. 2271-2288 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die allgemeinen Methoden, welche für das Studium der Polymerisation und der Copolymerisation des Isobutens durch neue synkatalytische Systeme entwickelt wurden, werden beschrieben. Diese Systeme bestehen aus Alkylaluminiumhalogeniden zusammen mit Halogenen oder Interhalogen-Verbindungen. Die Ergebnisse vorläufiger Experimente werden beschrieben, welche dahin zielten, das wirksamste katalytische System im Hinblick auf Ausbeute und Molekulargewicht der Polymeren aufzufinden. Die besten Ergebnisse wurden mit den folgenden Kombinationen erzielt: (C2H5)2AlCl+Cl2, (C2H5)2AlCl+JCl und (C2H5)2AlJ+J2.
    Notes: The general procedures which were developed for the study of the polymerization and copolymerization of isobutene, initiated by novel syncatalytic systems based on dialkyl aluminium halides and halogens or interhalogen compounds, are described. The results of preliminary experiments on polymerization and copolymerization carried out with the goal of identifying the most promising catalytic systems from the point of view of efficiency and of polymer molecular weight are described briefly. The best results were obtained with the systems (C2H5)2AlCl+Cl2, (C2H5)2AlCl + ICl, and (C2H5)2AlI + I2.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1975.021760809
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  • 7
    Electronic Resource
    Electronic Resource
    Studies on polymerizations initiated by syncatalytic systems based on aluminium organic compounds, 3Part 2: cf.8.. Polymerization and copolymerization of isobutene initiated by diethylaluminium iodide and iodine (1975)
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 176 (1975), S. 2303-2317 
    Details
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Im Verlauf der Untersuchungen der Polymerisation des Isobutens und seiner Copolymerisation mit Isopren durch Diäthylaluminiumjodid + Jod in Pentan, Dichlormethan und Äthylchlorid, wurde der Einfluß der Konzentration der Reagenzien und der Temperatur auf die Ausbeute und das Molekulargewicht untersucht. Bei der Homopolymerisation des Isobutens, initiiert durch Diäthylaluminiumjodid + Jod, ist die Initiierung relativ langsam und führt zu nicht-stationären Reaktionen. Die Reaktion des Initiators mit dem Co-Initiator in Abwesenheit des Monomers führt zu Produkten (wahrscheinlich Äthylaluminiumdijodid). welche eine rasche, unvollständige Polymerisation des hinzugefüglen Isobutens verursachen.
    Notes: The polymerization of isobutene and its copolymerization with isoprene, initiated by diethylaluminium iodide + iodine was studied in pentane, dichloromethane, and chloroethane, and the influence of the concentrations of the reagents and of the temperature on the copolymer yield and molecular weight was investigated. In the homopolymerization of isobutene initiated by diethylaluminium iodide+iodine the initiation is a comparatively slow process leading to non-stationary reactions. The interaction between initiator and co-initiator in the absence of monomer produces products (most probably ethylaluminium diiodide) which, on addition of monomer, cause fast, incomplete polymerization of isobutene.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/macp.1975.021760811
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  • 8
    Electronic Resource
    Electronic Resource
    Glass transition temperatures of some linear polymers containing phenyl side groups (1971)
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 1133-1145 
    Details
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The glass transition temperatures of a number of poly(vinyl phenyl ketones), poly-(vinyl benzoates), and poly(phenyl acrylates) have been measured by a refractometric method. The effects exerted on Tg by the nature and position of the ring substituents and by the different groups binding the pendant phenyl rings to the polyvinyl chain are discussed. The importance of knowledge of the side-group motions in the glassy state for the interpretation of glass temperature data is emphasized.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1971.160090609
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  • 9
    Electronic Resource
    Electronic Resource
    Physicochemical properties of poly(allylammonium acrylate) complexes obtained by radical template polymerization (1994)
    Weinheim : Wiley-Blackwell
    Macromolecular Rapid Communications 15 (1994), S. 983-990 
    Details
    ISSN: 1022-1336
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/marc.1994.030151212
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  • 10
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    Molecularly imprinted submicronspheres for applications in a novel model biosensor-film (2010)
    Elsevier
    Details
    Publication Date: 2010-09-01
    Print ISSN: 0925-4005
    Electronic ISSN: 1873-3077
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Published by Elsevier
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