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  • 1
    Electronic Resource
    Electronic Resource
    Monte-Carlo-Simulation der Polycyclotrimerisierung difunktioneller aromatischer Cyansäureester (1987)
    Weinheim : Wiley-Blackwell
    Acta Polymerica 38 (1987), S. 16-21 
    Details
    ISSN: 0323-7648
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: A Monte Carlo model for the simulation of the process of network building by polycyclotrimerization of difunctional monomers basing on the reaction mechanism of the polycyclotrimerization of aromatic dicyanates was developed. The experimental dependences of the average molar mass, the mass fractions of the first oligomers and of the gel fraction on the conversion of functional groups, measured for the reaction of 2, 2-bis(4-cyanatophenyl) propane in bulk, can be well fitted by the model. Furthermore, the possiblities of the simulation of intramolecular cyclizations and substitution effects are discussed.
    Notes: Auf Basis des Reaktionsmechanismus der Polycyclotrimerisierung aromatischer Dicyanate wurde ein Monte-Carlo-Modell zur Simulation der Netwerkbildung durch Polycyclotrimerisierung difunktioneller Monomere entwickelt. Die experimentell ermittelten Abhängigkeiten der mittleren Molmasse, der Massenanteile der ersten Oligomere und des Gelanteils vom Umsatz der funktionellen Gruppen bei der Reaktion von 2, 2-Bis (4-cyanatophenyl) propan in Schmelze werden durch das Modell gut erfaßt. Weiterhin werden Möglichkeiten der Simulation von intramolekularen Cyclisiierungen und Substituenteneffekten diskutiert.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/actp.1987.010380104
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  • 2
    Electronic Resource
    Electronic Resource
    Reaktionen polyfunktioneller Cyansäureester mit polyfunktionellen Glycidethern. 2. ReaktionsmodellTeil 1: siehe [1] (1989)
    Weinheim : Wiley-Blackwell
    Acta Polymerica 40 (1989), S. 397-401 
    Details
    ISSN: 0323-7648
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: A model of the reaction between glycidylethers and aromatic cyanates is established. It was found that the trimerization of cyanates, the insertion of glycidylethers, the isomerisation of alkylcyanurates, the oxazolidinone build up, the abstraction of the phenols, and the phenol/glycidylether-addition are the main reactions.
    Notes: Ein Reaktionsmodell der Umsetzung von Glycidethern mit aromatischen Cyansäureestern wird begründet. Als Hauptreaktionen wurden die Trimerisierung der Cyansäureester, die Einschubreaktion der Glycidether in die Cyanuratstruktur, die Isomerisierung der Alkylcyanurate, die Oxazolidinonbildung, die Phenolabspaltung und die Phenol/Glycidether-Addition gefunden.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/actp.1989.010400608
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  • 3
    Electronic Resource
    Electronic Resource
    Analytik von Prepolymeren und Polymeren aromatischer Cyansäureester. 3. Differential Scanning CalorimetrieTeil 2: Acta Polymerica 37 (1986) 221-223. (1986)
    Weinheim : Wiley-Blackwell
    Acta Polymerica 37 (1986), S. 604-606 
    Details
    ISSN: 0323-7648
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: By DSC-experiments with constant heating rate or under isothermal conditions the complex character of the thermal polycyclotrimerisation of 2,2-bis(4-cyanatophenyl)propane in bulk is shown. An activation energy of 80 kJ/mol for the first order brutto kinetics is calculated by several methods.
    Notes: Aus DSC-Messungen mit konstanter Heizrate und unter isotherman Bedingungen wird der komplexe Charakter der thermischen Polycyclotrimerisierung von 2,2-Bis(4-cyanatophenyl)propan in der Schmelze ersichtlich. Für die Bruttoreaktion 1. Ordnung wird nach verschiedenen Auswertemethoden eine Aktivierungsenergie von 80 kJ/mol erhalten.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/actp.1986.010371002
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  • 4
    Electronic Resource
    Electronic Resource
    Kinetical structural model for the network build-up during the reaction of cyanic acid esters with glycidyl ethers. 2. Application of DCBA/DGEBA-systems (1990)
    Weinheim : Wiley-Blackwell
    Acta Polymerica 41 (1990), S. 535-538 
    Details
    ISSN: 0323-7648
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Das in einer früheren Arbeit publizierte kinetisch/strukturelle Modell wird auf den Netzwerkaufbau durch Coreaktion von 2,2-Bis(4-cyanatophenyl)propan mit 2,2-Bis(4-glycidyloxyphenyl) propan in der Schmilze angewendet. Die relativen Geschwindigkeitskonstanten der Hauptreaktionen, die die freien Parameter des Modells darstellen, werden für diesen Fall identifiziert, und die gute Übereinstiummung zwischen Theorie und Experiment wird gezeigt.
    Notes: The previously published kinetical structural model is applied to the network build-up during the coreaction of 2,2-bis(4-cyanatophenyl) propane with 2,2-bis(4-glycidyloxyphenyl) propane in bulk. The relative rate constants of the main reactions, which act as the free parameters of the model, were identified for this case, and the good agreement between theory and experiment is shown.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/actp.1990.010411006
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  • 5
    Electronic Resource
    Electronic Resource
    Kinetics and modelling of thermal polycyclotrimerization of aromatic dicyanates (1986)
    Weinheim : Wiley-Blackwell
    Acta Polymerica 37 (1986), S. 715-719 
    Details
    ISSN: 0323-7648
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Kinetik der thermischen Polycyclotrimerisierung von 2,2-Bis(4-cyanatophenyl)propan wurde mit Hilfe von DSC und IR-Spektroskopie untersucht. Der autokatalytische Charakter der Reaktion wurde durch Modellierung der Umsatz-Zeit-Kurven bei Zusatz difinierter Mengen der nachgewiesenen Zwischenprodukte aufgeklärt. Weiterhin wurden quantitative Beziehungen zwischen Reinheitsgrad des Dicyanats, Geschwindigkeit der Bruttoreaktion, Lage des DSC-Maximums und B-Zeit gefunden.
    Notes: The kinetics of polycyclotrimerization of 2,2-bis(4-cyanatophenyl)propane was analyzed by differential scanning calorimetry and IR spectroscopy. The autocatalytic character of the reaction was elucidated by modelling the conversion-time curves of systems with definite admixtures of the found intermediate products. Furthermore, quantitative relations between the purity of the dicyanate, the rate of the brutto reaction, the temperature of the DSC maximum, and the B-time of the resin were found.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/actp.1986.010371112
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  • 6
    Electronic Resource
    Electronic Resource
    Reaction of dicyanates with monophenols  -  modeling of network buildup (1995)
    Weinheim : Wiley-Blackwell
    Acta Polymerica 46 (1995), S. 241-246 
    Details
    ISSN: 0323-7648
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Chemical as well as structural modifications of highly branched polycyanurates can be achieved by using the reaction of dicyanates with monofunctional phenols. The key products of this reaction are iminocarbonic esters formed by addition of cyanato and phenolic groups. Two mechanisms are discussed for the second reaction step: an addition of two cyanato groups and an iminocarbonic ester (Route A) and a stepwise addition of iminocarbonic esters (Route B). The crucial difference between the two reactions is the number of abstracted phenolic groups per formation of one triazine ring: one for Route A and three for Route B. The effects of these reaction mechanisms on the gelation behavior and network buildup are studied theoretically with the help of cascade theory as well as experimentally by the reaction of dicyanate of bisphenol A with five different monophenols. The results clearly show that only with a model which is based on Route B can both the critical conversions at the gelation threshold and the gel fractions be modeled quantitatively. Furthermore, phenols with low pKa values were found to have an increased tendency of incorporation into the network.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/actp.1995.010460305
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  • 7
    Electronic Resource
    Electronic Resource
    Remark on the approximate character of the kinetic/structural model for the cyanate-epoxy network build-up (1989)
    Weinheim : Wiley-Blackwell
    Acta Polymerica 40 (1989), S. 679-680 
    Details
    ISSN: 0323-7648
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/actp.1989.010401016
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  • 8
    Electronic Resource
    Electronic Resource
    Polymelamines from cyanurates and amines, 1. Reaction kinetics of model compounds (1998)
    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 199 (1998), S. 103-108 
    Details
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of the reaction of 2,4,6-triphenoxy-1,3,5-triazine with octylamine in N-methyl-2-pyrrolidone at temperatures between 10°C and 190°C was analyzed by HPLC. Data analysis with the help of a mathematical model showed first order kinetics in each reaction component for the three successive substitutions at the triazine ring. The calculated rate constants differ by orders of magnitude from each other, and their ratios show a pronounced temperature dependence due to the differing activation energies of 27,53 and 82 kJ · mol-1
    Additional Material: 8 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Cyclotrimerization reactivities of mono- and difunctional cyanates (1998)
    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 199 (1998), S. 2417-2423 
    Details
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The influence of substituents of several mono- and difunctional cyanates on their cyclotrimerization behaviour has been studied by several methods. Shifts of gel point and gel fractions at full conversion in dependence on the substituent were detected for coreactions of a dicyanate with monofunctional cyanates. Critical fractions of monocyanate groups in the range of 50 mol-% for the absence of gelation were measured and could be described quantitatively by a model that is based on reaction kinetics and network statistics. Reactivity differences in dependence on substituents are also reflected in the distribution of homo- and mixed trimers at full conversion of paris of different monofunctional cyanates as measured by high-performance liquid chromatography (HPLC). This distribution follows a simple binomial scheme for cyanates with equal reactivity, whereas remarkable deviations occur, if one of the monomers reacts faster than the other. Besides, a qualitative reactivity gradation of the used cyanates was found on the basis of differential scanning calorimetry (DSC) peak temperatures, where the reaction of each cyanate was catalyzed by the same amount of a certain phenol. Finally, the shift of the OH band of several phenols caused by association with cyanate groups, measured by FTIR, was related to the data obtained from gelation, trimer distribution and DSC experiments to establish an easy and reproducible method for comparing the reactivity of cyanate monomers.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Zur Bestimmung der Molmassenverteilung verzweigter Polyphenylchinoxaline durch Gelpermeationschromatographie und ViskosimetrieProfessor Dr. sc. nat. Horst Frommelt zum 60. Geburtsag gewidmet (1985)
    Weinheim : Wiley-Blackwell
    Acta Polymerica 36 (1985), S. 16-21 
    Details
    ISSN: 0323-7648
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Molecular weight distributions of branched poly(phenylquinoxa1ines) synthesized by polycondensation of aromatic bis(l,2-diamines) with bis- and tris(l,2-diketones) were calculated based on a special a-priori branching model from gelchromatographic and viscosimetric data. Under the rcactioti conditions considered random reaction of all functional groups is suggested.
    Notes: Die Molmassenverteilungen von durch Polykondensation aromatischer Bis(1,2-diamine) mit Bis- und Tris(1,2-diketonen) synthetisierten verzweigten Polyphenylchinoxalinen wurden auf der Grundlage eines speziellen a-priori-Verzweigungsmodells aus gelchromatographischen und viskosimetrischen Daten berechnet. Damit kann für die angewendeten Synthesebedingungen eine zufällige Reaktion aller funktionellen Gruppen angenommen werden.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/actp.1985.010360104
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