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  • 1
    Publication Date: 1977-11-01
    Print ISSN: 0372-820X
    Electronic ISSN: 1435-1536
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Published by Springer
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  • 2
    Publication Date: 1977-11-01
    Print ISSN: 0372-820X
    Electronic ISSN: 1435-1536
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Published by Springer
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 255 (1977), S. 1144-1144 
    ISSN: 1435-1536
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 255 (1977), S. 1144-1144 
    ISSN: 1435-1536
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 156 (1972), S. 297-310 
    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: The polymerization of acrylonitrile, methyl acrylate, methyl methacrylate, α-chloromethyl acrylate and α-bromo methyl acrylate in dimethylformamide has been investigated using α.α′-azobisisobutyronitrile as initiator. The following relations have been derived at 60°C: for methyl acrylate v = 15.15·10-4·[I]0.5·[M], for methyl methacrylate v = 3.46·10-4·[I]0.5·[M], for α-chloro methyl acrylate v = 5.25·10-4·[I]0.5·[M], and for α-bromo methyl acrylate v = 4.12·10-4·[I]0.5·[M]. It has been found that (kp/kt0.5)60 is 14.4·10-2 for α-chloro methyl acrylate and 12.15·10-2 for α-bromo methyl acrylate. The relation between the kinetic data obtained and the HAMMETT σp constants has been discussed for the substituents in α-position to the double bond which are considered to be the characteristic parameters for the chemical structure of the monomers.
    Notes: Die Polymerisation von Acrylnitril, Methylacrylat, Methylmethacrylat, α-Chlor-methylacrylat und α-Brom-methylacrylat wurde in Dimethylformamidlösung mit α.α′-Azobisisobutyronitril als Initiator untersucht. Dabei ergaben sich für eine Temperatur von 60°C folgende Beziehungen: Für Methylacrylat v = 15,15·10-4·[I]0,5·[M], für Methylmethacrylat v = 3,46·10-4·[I]0,5·[M], für α-Chlor-methylacrylat v = 5,25·10-4·[I]0,5·[M] und für α-Brom-methylacrylat v = 4,12·10-4·[I]0,5·[M]. Es wurde gefunden, daß (kp/kt0,5)60 für α-Chlor-methylacrylat 14,4·10-2 und für α-Brom-methylacrylat 12,15·10-2 beträgt.Der Zusammenhang zwischen den erhaltenen kinetischen Daten und den HAMMETT-Konstanten σp für die Substituenten in α-Position zur Doppelbindung als die für die chemische Struktur der Monomeren bezeichnenden Parameter wurde erörtert.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 156 (1972), S. 311-320 
    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: Relationships between the copolymerization rate and the composition of monomer mixture have been evaluated for the following systems : acrylnitrile/methyl acrylate, acrylnitrile/methyl methacrylate, acrylnitrile/α-chloro methyl acrylate, and acrylnitrile/α-bromo methyl acrylate. The copolymerizations were carried out in dimethylformamide at 6O°C in the presence of azobisisobutyronitrile. The constants of cross termination were calculated from the equation of the copolymerization rate.
    Notes: In Abhängigkeit von der Zusammensetzung der Monomermischung wurden für folgende Systeme die Copolymerisationsgeschwindigkeiten in Dimethylformamidlosung bei 60°C gemessen : Acr ylnitril/Methylacrylat, Acrylnitril/Methylmethacr ylat, Acrylnitril/α-Chlor-methylacrylat und Acrylnitril/α-Brom-methylacrylat. Als Initiator diente α.α′-Azobisiso-butyronitril. Die Konstanten für die gekreuzte Abbruchsreaktion wurden aus der Gleichung für die Copolymerisationsgeschwindigkeit berechnet.
    Additional Material: 2 Tab.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 176 (1975), S. 2971-2980 
    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: The bulk polymerization of 3,3,3-trichloropropene with dicyclohexylperoxidicarbonate as initiator is studied. In the temperature range between 303 and 343 K, the initial rate of polymerization follows the relation: \documentclass{article}\pagestyle{empty}\begin{document}$$ v = k[{\rm Initiator}]^{0,5} [{\rm Monomer}] $$\end{document}For the temperature dependence of the overall rate constant the relation \documentclass{article}\pagestyle{empty}\begin{document}$$ k = 5,8 \cdot 10^8 \exp [( - 82,124\,{\rm kj}\,{\rm mol}^{{\rm - 1}} )/(RT)]{\rm dm}^{3/2} \,{\rm mol}^{ - 1/2} \,{\rm s}^{ - 1}$$\end{document} is valid. The rates of the initiation of the polymerization are determined by the inhibitor method with toluenechinon (2-methyl-l,4-benzoquinone). The efficiency of the initiator is 0,25±0,03 and the rate constants of propagation and termination, kp and kt, obey the relation: \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{\rm p} /k_{\rm t}^{0,5} = 15,05\,\exp [( - 20,112\,{\rm kj}\,{\rm mol}^{{\rm - 1}} )/(RT)]\,{\rm dm}^{{\rm 3/2}} \,{\rm mol}^{{\rm - 1/2}} {\rm s}^{{\rm - 1/2}}$$\end{document}
    Notes: Es wird die Polymerisation des 3,3,3-Trichlorpropens mit Dicyclohexylperoxydicarbonat als Initiator in Substanz untersucht. Im Temperaturbereich von 303-343 K gehorcht die Anfangsgeschwindigkeit der Polymerisation der Beziehung \documentclass{article}\pagestyle{empty}\begin{document}$$ v = k[{\rm Initiator}]^{0,5} [{\rm Monomer}] $$\end{document}Für die Temperaturabhängigkeit der Bruttogeschwindigkeitskonstante gilt: \documentclass{article}\pagestyle{empty}\begin{document}$$ k = 5,8 \cdot 10^8 \exp [( - 82,124\,{\rm kj}\,{\rm mol}^{{\rm - 1}} )/(RT)]{\rm dm}^{3/2} \,{\rm mol}^{ - 1/2} \,{\rm s}^{ - 1}$$\end{document} Die Initiierungsgeschwindigkeiten wurden mit der Inhibitormethode unter Verwendung von Toluchinon (2-Methyl-1,4-benzochinon) als Inhibitor bestimmt; der Radikalausbeutefaktor („efficiency“) beträgt 0,25±0,03. Zwischen den Geschwindigkeitskonstanten für Wachstum und Abbruch, kp und kt, besteht die Beziehung: \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{\rm p} /k_{\rm t}^{0,5} = 15,05\,\exp [( - 20,112\,{\rm kj}\,{\rm mol}^{{\rm - 1}} )/(RT)]\,{\rm dm}^{{\rm 3/2}} \,{\rm mol}^{{\rm - 1/2}} {\rm s}^{{\rm - 1/2}}$$\end{document}
    Additional Material: 2 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 176 (1975), S. 2981-2986 
    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: A study of the kinetics of the bulk copolymerization of 3,3,3-trichloropropene (TClP) with styrene initiated by dicyclohexylperoxidicarbonate at 60°C was carried out. The dependence of the copolymerization rate on the composition of the monomer mixture was determined. Assuming a linear relationship between the initiation rate vi and the composition of the monomer mixture, the parameter Φ (relative constant of alternating termination) was calculated to increase not monotonically from 81 to 243 as the mole fraction of styrene in the monomer mixture varies from 0,136 to 0,851. Experimentally it was demonstrated, however, that vi does not depend linearly on the composition of the monomer mixture. With the experimental values for vi, Φ was calculated to be 72±10, independent of the composition of the monomer mixture. The monomer reactivity ratios for the system TClP/styrene are found to be r1 (TClP)=0,017 and r2 (styrene)=7,8.
    Notes: In dieser Arbeit werden Untersuchungsergebnisse über die Kinetik der mit Dicyclohexyl-peroxidicarbonat initiierten Substanz-Copolymerisation von 3,3,3-Trichlorpropen (TClP) mit Styrol bei 60°C mitgeteilt. Es wurde die Abhängigkeit der Copolymerisationsgeschwindigkeit von der Zusammensetzung des Monomergemisches bestimmt. Unter Annahme einer linearen Abhängigkeit der Initiierungsgeschwindigkeit vi von der Zusammensetzung des Monomergemisches wurde der Parameter Φ (relative Konstante des alternierenden Abbruchs) berechnet, wobei mit Änderung des Molenbruchs von Styrol in der Mischung von 0,136 bis 0,851 die Konstante Φ nicht monoton von 81 bis 243 ansteigt. Experimentell wurde jedoch gezeigt, daß vi keine lineare Funktion der Zusammensetzung der Monomermischung ist. Mit den experimentellen Werten für vi folgt unabhängig von der Zusammensetzung des Monomergemisches für Φ ein Wert von 72±10. Die Copolymerisationsparameter für das System TClP/Styrol betragen r1 (TClP)=0,017 und r2 (Styrol)=7,8.
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  • 9
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 1643-1655 
    ISSN: 0887-624X
    Keywords: radical polymerization ; initiation ; AIBN decomposition ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The solvation effect in the thermal decomposition of a radical initiator (AIBN) in monomer-solvent mixtures is discussed. Equations were derived which comprise the initiator decomposition constant as a function of the monomer mole fraction for chosen types of solvation. In addition, equations were deduced presenting the concentrations and partial relative decomposition rates for the solvated initiator species as a function of the monomer mole fraction. The equations obtained were compared to the experimental literature data and possible dependences of decomposition constants on monomer concentration were simulated for various solvated species. The simulated relationships were found to be straight lines, curves of saturated type (possessing a plateau), S-shaped curves, and maximum or minimum curves. © 1995 John Wiley & Sons, Inc.
    Additional Material: 16 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 1637-1642 
    ISSN: 0887-624X
    Keywords: AIBN decomposition ; radical initiation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition rate constant of AIBN (kd) in N,N-dimethylformamide (DMF)/methyl methacrylate (MM) mixtures of various compositions at 60°C is studied. The kd value is 6.45 × 10-4min-1 for pure DMF and 7.20 × 10-1 min-1 for pure methyl methacrylate. The kd values of DMF/MM mixtures were found to be dependent on the mixture composition. This dependence is not a linear function of the monomer mole fraction, but has a minimum at ca. 20 30 mol% of MM. The relationship between the AIBN decomposition rate constant and the monomer mole fraction was interpreted on the basis of solvation of the initiator molecules. © 1995 John Wiley & Sons, Inc.
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