ISSN:
1022-1344
Keywords:
Chemistry
;
Polymer and Materials Science
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
The pulsed laser polymerization technique is now a well accepted method to determine propagation rate coefficients for radical polymerization from molar mass distributions resulting from intermittent initiation. A simplified apparatus for the periodic photoinitiation is used which is much less expensive than the laser equipment. The usefulness of the simplified equipment was proved by the determination of kp for styrene at technically relevant temperatures up to 130°C for the first time. Furthermore, careful inspection of the molar mass distribution (mmd) reveals that depending on the reaction conditions, inflection points (Li) can not only be found at integer multiples of kp • to • [M] but also at 0.5i • kp • to • [M], i = 1, 2, 3, … . A rule to find the inflection points leading to correct values for kp is proposed. It is shown that the shape of the mmd inter alia depends on the amount of primary radical termination compared to the termination reaction between growing chains. With dominant primary termination, the maxima of the distribution will give the correct kp, whereas in the absence of primary termination the inflection points should be used. Experimental conditions like initiator concentration, light intensity etc. may influence the position of the Li at least to some extent, and so may give a small but principal error or uncertainty in kp. A new mathematical method for the time-dependent simulation of the resulting mmd is presented which allows the calculations being performed on a PC within an acceptable time.
Additional Material:
15 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/mats.1997.040060207
