ISSN:
0887-624X
Keywords:
α-,β,β-, and α,β,β-deuterated polyacrylonitrile
;
polyacrylonitrile stabilization
;
deuterium isotope effects
;
Chemistry
;
Polymer and Materials Science
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
A series of α-, β,β-, and α,β,β-deuterium-labelled acrylonitrile monomers were prepared and polymerized. Secondary deuterium isotope effects on the polymerization and on the pyrolysis reactions that precede carbon fiber formation were observed. When deuterium is in the α-position, the polymerization rate is greater and the molecular weight is higher. It is proposed that either the propagation rate constant or both that constant and the termination rate constant are increased on deuterium substitution. In differential scanning calorimetry, the polyacrylonitrile exotherm occurs at higher temperatures and is narrower when deuterium is substituted at the α-position. On the other hand, the thermal gravimetric analysis activation energy for weight loss of polymer at temperatures below the acrylic exotherm is lower when deuterium is in the α-position, relative to the α-hydrogen polymers. As there is no correlation between the weight loss energy of activation and the various exotherm parameters, the weight loss energy of activation and the various exotherm parameters, the weight loss and exotherm are considered to be independent events. Examination of the distribution of deuterium substituted ammonia species evolved during 100-240°C thermal treatment of the α-and β, β-deuterated polyacrylonitriles provides a clear indication that both the α- and β-positions are directly involved in hydrogen migration to nitrogen, but the mechanism of ammonia generation remains unclear. © 1995 John Wiley & Sons, Inc.
Additional Material:
9 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/pola.1995.080331214
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