ISSN:
0360-6376
Keywords:
Physics
;
Polymer and Materials Science
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The reaction of 1,3-cycloheptadiene (1,3-CHpD) with acrylonitrile (AN) in the presence of ZnCl2 leads spontaneously to the simultaneous formation of an alternating copolymer and a small amount of cycloadduct. The copolymer has a predominantly cis-1,4-structure. The formation of the charge - transfer complex between 1,3-CHpD and (AN)c (AN coordinated to ZnCl2) in AN was detected by ultraviolet (UV) spectroscopy. The activation energies for the cycloaddition and for the copolymerization under the conditions used were determined to be 17.6 (in the presence of 1,1-diphenyl-2-picrylhydrazyl) and 16.3 kcal/mole, respectively. The rate of copolymerization in AN was found to depend on the 1.5th power of the concentrations of (AN)c and of 1,3-CHpD. Oxygen and UV irradiation causes an acceleration of the copolymerization only. On the basis of these results the mechanism of the spontaneous copolymerization is discussed and its relation to the cycloaddition in systems of 1,3-cyclodienes and AN in the presence of ZnCl2 is mentioned.
Additional Material:
8 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/pol.1981.170190229
