ISSN:
0025-116X
Keywords:
Chemistry
;
Polymer and Materials Science
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Description / Table of Contents:
Die durch Gammastrahlen initiierte Polymerisation von Formaldehyd in Toluol und Äthylbromid bei -50 bis -80°C wird untersucht und die Kinetik ausführlicher als in der ersten Arbeit2 diskutiert.Die Bruttoreaktion ist von 3. Ordnung bezüglich des Monomeren und von 1. Ordnung bezüglich der Strahlungsdosis; das Molekulargewicht dagegen ist weitgehend unabhängig von der Strahlungsdosis und von der Monomerkonzentration. Es wird angenommen, daß die Polymerisation nach einem ionischen Mechanismus abläuft, wobei das Molekulargewicht im wesentlichen durch eine Kettenübertragung mit dem Monomeren bestimmt wird.
Notes:
This paper presents a more detailed discussion on the kinetics of formaldehyde polymerization under gamma-irradiation than the previous paper2. Polymerization took place in toluene and ethyl bromide and within the range of -50°∼-80°C.The overall reaction is approximately third-order with respect to the monomer. The average molecular weight of the polyoxymethylene obtained is little dependent on the initial concentration of the monomer and on dose rate. The reaction is approximately first order with respect to dose rate. It is believed from the facts obtained here that the polymerization, in which the transfer process of growing chain to monomer is mainly responsible for governing the molecular weight, should proceed predominantly by an ionic mechanism.A study of the influence of various additives upon the polymerization shows the following results. These additives are classified in four groups with respect to their qualities, the first group having influence only upon the polymerization rate (e.g., diphenylpicrylhydrazyl), the second only upon the molecular weight (water), the third upon both of these factors (methyl formate, methyl acetate, ethyl acetoacetate, polystyrene powder, and tetrahydrofuran), and the last having no influence upon both of these factors (oxygen, carbon monoxide, nitrobenzene, and naphthalene).The apparent activation energy is estimated to be 4.15 kcal/mole from rate of polymerization, -3.50 kcal./mole from average degree of polymerization.
Additional Material:
10 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/macp.1965.020830103
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