Investigation of autoacceleration effects during the solution polymerization of styrene

Autor:	J. E. Glass, Nathan L Zutty
Rok vydání:	1966
Předmět:	Kinetic chain length Chain-growth polymerization Polymerization Chemistry Autoacceleration Radical polymerization technology industry and agriculture General Engineering Living polymerization Solution polymerization macromolecular substances Degree of polymerization Photochemistry
Zdroj:	Journal of Polymer Science Part A-1: Polymer Chemistry. 4:1223-1243
ISSN:	1542-9350 0449-296X
DOI:	10.1002/pol.1966.150040521
Popis:	The possibility of obtaining increases in the rate and degree of polymerization through a decrease in the termination rate in nonviscous, homogeneous solution polymerizations of styrene has been investigated. Decreases in the termination rate were achieved through decreasing segmental diffusion of the propagating macroradical by greater occlusion, on the average, of the radical in the coiled polymeric chain. Coiling of the polymeric chain was effected by polymerizing styrene in thermodynamically poor (θ) solvents near the θ temperature for polystyrene. Examples of such systems are diethyl oxalate at 51.5°C. and cyclohexane at 34.6°C. Polymerization under these conditions did lead to a decrease in the kt/kp2 kinetic ratio; this decrease resulted in increases in the degree of polymerization, but changes in the rate of polymerization, in contrast to the marked increases noted in viscous solution or heterogeneous polymerizations, were not observed. Possible explanations for the latter observations are discussed.
Databáze:	OpenAIRE
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