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The thermal decomposition of poly(vinylidene chloride) in the solid state
Author(s) -
Bohme R. D.,
Wessling R. A.
Publication year - 1972
Publication title -
journal of applied polymer science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.575
H-Index - 166
eISSN - 1097-4628
pISSN - 0021-8995
DOI - 10.1002/app.1972.070160713
Subject(s) - polymer , activation energy , polymerization , thermal decomposition , monomer , materials science , decomposition , polymer chemistry , kinetics , order of reaction , chemical engineering , polyvinyl chloride , lamellar structure , annealing (glass) , reaction rate constant , chemistry , organic chemistry , composite material , physics , engineering , quantum mechanics
The rate of decomposition of PVDC is sensitive to differences in the method of preparation of the polymer. Polymers prepared by mass polymerization of very pure monomer were most stable. Emulsion polymerized PVDC degraded the fastest. The activation energy for the latter was 34.4 kcal/mole. Over the range of 130°–190°C, the rate of decomposition increases with reaction time to ∼10% HCl evolved. Beyond this point, the reaction follows first‐order kinetics. The first‐order rate is independent of molecular weight. Lamellar crystals of PVDC degrade at a higher rate than “as polymerized” powders. This may be due in part to annealing of the crystals in the degradation temperature range; but it also results from a sensitization of the polymer to thermal degradation from exposure to the polar solvents used for recrystallization. A mechanism is proposed to account for these observations.