Intermolecular hydrogen transfer reactions in the mass spectra of dialkyl malonates

1972 ◽  
Vol 94 (11) ◽  
pp. 3865-3869 ◽  
Author(s):  
Mary H. Wilson ◽  
James A. McCloskey
Keyword(s):  
Mass Spectra ◽  
Hydrogen Transfer ◽  
Transfer Reactions ◽  
Intermolecular Hydrogen Transfer ◽  
Hydrogen Transfer Reactions

Thermal Decomposition Kinetics of Functionalized Polynorbornene

2002 ◽  
Vol 17 (3) ◽  
pp. 632-640 ◽  
Author(s):  
Michael D. Wedlake ◽  
Paul A. Kohl
Keyword(s):  
Thermal Decomposition ◽  
Mass Spectra ◽  
Hydrogen Transfer ◽  
Transfer Reaction ◽  
Transfer Reactions ◽  
Thermogravimetric Analyses ◽  
First Order ◽  
Degradation Reaction ◽  
Intermolecular Hydrogen Transfer ◽  
Kinetics Of

The mechanism and kinetic parameters for the thermal decomposition of four functionalized addition-polymerized polynorbornenes were studied by dynamic and isothermal thermogravimetric analyses and by mass spectrometry. The dynamic and isothermal thermogravimetric analyses showed a first-order degradation reaction mechanism with an activation energy of 229.6 ± 12.5 kJ/mol. Based on the polymer structure, reference mass spectra for related molecules, and a cross-comparison of the mass spectra, the backbone, free-radical scission mechanism was found to occur by cleavage of the linkages between bicyclic rings and the production of volatile monomer and oligomers. The degradation of polynorbornene occurred via a depropagation and transfer reaction process. Initially, the depropagation pathway was preferred, but with increasing conversion, intra- and intermolecular hydrogen transfer reactions dominated.

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