ISSN:
0449-296X
Keywords:
Physics
;
Polymer and Materials Science
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The polymerization of trioxane catalyzed by stannic chloride (SnCl4) in ethylene dichloride was studied and compared with the results obtained with boron trifluoride etherate, BF3·O(C2H5)2, as catalyst. Under the same conditions, the polymerization rate was larger with SnCl4 than with BF3·O(C2H5)2, while at a fixed polymer yield the molecular weight of the polymer obtained by SnCl4 was lower than with the BF3·O(C2H5)2 catalyzed reaction. The overall activation energy of trioxane polymerization with SnCl4 was 11.0 ± 0.8 kcal/mole. The kinetic orders of catalyst and monomer were determined to be close to 2 and 4, respectively. A certain amount of tetraoxane was also produced in an early stage of the polymerization with SnCl4 similar to BF3·O(C2H5)2-catalyzed reaction. However, the maximum amount of tetraoxane produced at 30°C was larger with SnCl4 than with BF3·O(C2H5)2. In addition, a ten-membered ring compound (pentoxane) was isolated in the solution polymerization of trioxane catalyzed by both SnCl4 and BF3·O(C2H5)2. The confirmation of pentoxane formation is strong evidence for the back-biting reaction mechanism.
Additional Material:
10 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/pol.1968.150061107
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