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  • 1
    Digitale Medien
    Digitale Medien
    Characterization of Reacting Polymer Systems by Temperature-Modulated Differential Scanning Calorimetry (1998)
    Springer
    Journal of thermal analysis and calorimetry 54 (1998), S. 585-604 
    Details
    ISSN: 1572-8943
    Schlagwort(e): epoxy resin ; inorganic polymer glass ; reaction-induced phase separation ; reaction mechanism ; TMDSC ; unsaturated polyester resin
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The benefits of temperature-modulated differential scanning calorimetry to characterize reacting polymers are illustrated for different experimental systems. The effects of combined isothermal and non-isothermal cure paths on (de)vitrification, mobility-restricted reactions, and relaxation during vitrification are discussed for anhydride- and amine-cured epoxies. The simultaneous measurement of heat capacity, heat flow, and heat flow phase provides an excellent tool for mechanistic interpretations. The influence of the metakaolinite particle size on the production of inorganic silicate-metakaolinite polymer glasses is treated as an example. These principles are further illustrated for primary and secondary amine-epoxy step growth reactions, and for styrene-cured unsaturated polyester chain growth reactions with ‘gel effect’. Finally, the effects of isothermal cure and temperature on reaction-induced phase separation in a polyethersulfone modified epoxy-amine system are highlighted.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1023/A:1010150711172
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  • 2
    Digitale Medien
    Digitale Medien
    TMDSC and Dynamic Rheometry, Gelation, Vitrification and Autoacceleration in the Cure of an Unsaturated Polyester Resin (2000)
    Springer
    Journal of thermal analysis and calorimetry 59 (2000), S. 305-318 
    Details
    ISSN: 1572-8943
    Schlagwort(e): autoacceleration ; dynamic rheometry ; gelation ; gel effect ; TMDSC ; unsaturated polyester resin ; vitrification
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The free radical cross-linking copolymerization of an unsaturated polyester resin with styrene is studied in isothermal conditions using temperature modulated differential scanning calorimetry (TMDSC) and dynamic rheometry. The dynamic rheometry measurements show that gelation occurs at a conversion below 5%, while TMDSC measurements show that an important autoacceleration starts near 60% conversion, giving rise to a maximum cure rate closely before the (partial) vitrification of the system near 80%. This indicates that the autoacceleration is not due to the sharp increase in bulk viscosity at gelation, but rather to a change in molecular mobilities at higher conversion.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1023/A:1010112718501
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  • 3
    Digitale Medien
    Digitale Medien
    Kinetics of the thermal reactions of bicyclo[4.2.2]deca-3,7-diene and endo-and exo-5-vinylbicyclo[2.2.2]oct-2-ene in the gas phase (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 251-257 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The kinetics of the thermal reactions of bicyclo[4.2.2]deca-3,7-diene (BDD) and endo- and exo-5-vinylbicyclo[2.2.2]oct-2-ene (endo- and exo-VBO) have been studied in the gas phase. The temperature range was 459-526 K for BDD, 476-563 K for endo-VBO, and 513-578 K for exo-VBO. The initial pressures were varied from 2 to about 40 torr. These compounds isomerize to cis-1,2,4a,5,8,8a-hexahydronaphtalene (HHN) and into each other, and decompose to 1,3-butadiene (BD) + cyclohexa-1,3-diene (CHD). The reactions are homogeneous and first order. Their rate constants (in s-1) are given by: where the superscripts represent the reagents and the subscripts the products. The heats of formation and the entropies of endo-VBO, exo-VBO, and BDD are estimated.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550140305
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  • 4
    Digitale Medien
    Digitale Medien
    Kinetics and mechanism of the addition of 1,3-butadiene to cyclohexa-1,3-diene in the gas phase (1982)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 14 (1982), S. 259-267 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The thermal reactions of 1,3-butadiene (BD) with cyclohexa-1,3-diene (CHD) have been studied in a static system between 437 and 526 K. The pressures of BD and CHD were varied from 61 to 397 torr and from 50 to 93 torr, respectively. The percentages of consumed BD and CHD were always kept lower than 14%. The reactions - in the order of importance - are All the reactions are homogeneous and of the first order with respect to the reagents. Their rate constants (in L/mol·s) are given by \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l} \log _{10} k_{{\rm HHN}} = - (25,370 \pm 70)/4.576T + (7.02 \pm 0.03) \\ \log _{10} k_{{\rm KNDO}} = - (24,840 \pm 50)/4.576T + (6.58 \pm 0.02) \\ \log _{10} k_{{\rm BDD}} = - (25,530 \pm 50)/4.576T + (6.61 \pm 0.02) \\ \log _{10} k_{{\rm EXO}} = - (26,760 \pm 50)/4.576T + (7.06 \pm 0.02) \\ \end{array} $$\end{document} A thermochemical analysis of a biradical mechanism is in agreement with these results.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550140306
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  • 5
    Digitale Medien
    Digitale Medien
    A biradical calculation model for the thermal dimerization of cyclohexa-1,3-diene in the gas phase (1985)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 17 (1985), S. 709-711 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550170612
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  • 6
    Digitale Medien
    Digitale Medien
    Gas phase kinetic and thermochemical data for endo- and exo-5-monosubstituted bicyclo[2.2.2]Oct-2-Enes (1986)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 18 (1986), S. 537-545 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The thermal reactions of endo- and exo-5-Y bicyclo[2.2.2]oct-2-enes (NYBO and XYBO) where Y = methyl, ethyl, and isopropyl have been studied in the gas phase between 567 and 695 K. For both isomers they are parallel first-order retro-Diels-Alder reactions with elimination of ethene (E) and monosubstituted ethene (YE).The observed Arrhenius parameters are used to discuss the mechanism and to estimate the heats of formation and the entropies of NYBO and XYBO. Group values are proposed for estimation of these thermochemical data for compounds of the same type by means of the methods of Benson.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550180504
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  • 7
    Digitale Medien
    Digitale Medien
    Kinetics, mechanism, and stereochemistry of Diels-Alder reactions of carbonyl-substituted ethenes with cyclohexa-1,3-diene in the gas phase (1987)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 1063-1072 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The kinetics of the Diels-Alder additions of CH2 — CHCHO, CH2—C(CH3)CHO, and CH2—CHC(CH3)O to cyclohexa-1,3-diene (CHD) have been studied in the gas phase. The stereochemistry and the mechanism of these reactions are discussed. In contrast with other Diels-Alder additions involving CHD as diene, a biradical mechanism does not fit the experimental results.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550191203
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  • 8
    Digitale Medien
    Digitale Medien
    Selectivity-reactivity correlations for thermal Diels-Alder reactions of cyclohexa-1,3-diene with substituted Ethenes in the gas phase (1989)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 967-976 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Selectivity-reactivity correlations are shown to support a biradical pathway for the gas phase thermal Diels-Alder reactions of cyclohexa-1,3-diene with substituted ethenes except for those involving a carbonyl group.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550211008
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  • 9
    Digitale Medien
    Digitale Medien
    Thermal dimerization of 1,3-butadiene: Kinetics of the formation of cis, cis-cycloocta-1,5-diene (1977)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 9 (1977), S. 283-293 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The thermal reaction of 1,3-butadiene (BD) has been studied between 464 and 557°K at pressures between 49 and 450 torr. The products are 4-vinylcyclohexene (VCH) and cis, cis-cycloocta-1,5-diene (COD), and their formations are second order. The rate constant (in 1/mol · sec) for VCH is given by \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}_{10} k_{\rm V} = - (24,530 \pm 120)/4.576T + (6.95 \pm 0.05) $$\end{document} and that for COD by \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}_{10} k_{\rm C} = - (28,440 \pm 100)/4.576T + (7.65 \pm 0.04) $$\end{document}The thermal reaction of COD has also been studied. The temperature was varied from 505 to 586°K and the pressure from 15 to 51 torr. The rate constants (in sec-1) for the formations of VCH and BD are given by \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l} {\rm log}_{10} k_{{\rm VCH}} = - (51,780 \pm 120)/4.576T + (15.34 \pm 0.05) \\ {\rm log}_{10} k_{{\rm BD}} = - (56,380 \pm 100)/4.576T + (16.46 \pm 0.04) \\ \end{array} $$\end{document}A biradical mechanism seems to fit these results. The heat of formation and the entropy of COD are estimated.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550090211
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  • 10
    Digitale Medien
    Digitale Medien
    Pyrolysis of 1,1,1-Trichloroethane in the absence and the presence of added HCl and/or CCl4 (1989)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 575-591 
    Details
    ISSN: 0538-8066
    Schlagwort(e): Chemistry ; Physical Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The title reaction has been studied in a static quartz reaction vessel between 587 and 658 K at pressures between 40 and 152 torr. The dehydrochlorination is the only significant reaction and is autoaccelerated by the produced HCl. Numerical modelling indicates that the Rice-Herzfeld mechanism, generally used for describing the pyrolysis of halogenated ethanes, has to be completed in the case of CC13CH3 with additional transfer reactions converting “dead” radicals into chain carriers and vice-versa. The numerical simulation fits the experimental results, in the absence as well as in the presence of different amounts of added HCl. The dehydrochlorination is also accelerated by the addition of CCl4, which can be explained in terms of additional elementary steps involving · CCl3 radicals.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/kin.550210708
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