ISSN:
0360-6376
Keywords:
Physics
;
Polymer and Materials Science
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The bulk polymerization of acrylonitrile (AN) initiated by copper (II) nitrate, Cu(II), in the absence of light has been studied. The rate of the AN polymerization may be expressed in the Cu(II) concentration range from 5 × 10-4 to 1 × 10-1 mole 1.-1 by the equation, Rp = k5[Cu(II)]0.68, where k5 = KAN[AN]/(1 + KAN[AN]). From the spectrophotometric measurements the values of 0.70 l./mole and 0.08 l, mole were obtained for the equilibrium constant at 20 and 60°C, respectively, KAN = [C]/[AN]-[Cu(II)], corresponding to the formation of the complex C from acrylonitrile and copper (II) nitrate. An addition of triphenylphosphine (C6H5)3P into the polymerization system reduces Rp, and no polymerization takes place at all provided [(C6H5)3P]/[Cu-(II)] ≧ 5. The retardation effect of (C6H5)3P on the polymerization of AN initiated by Cu(II) is attributed to a competitive reaction of Cu(II) with (C6H5)3P in which Cu(II) is reduced and the product of this reduction CuNO3·2(C6H5)3P is inactive with respect to the polymerization of AN.
Additional Material:
7 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/pol.1974.170121009
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