ISSN:
1022-1352
Keywords:
Chemistry
;
Polymer and Materials Science
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
Radical copolymerizations of ring-substituted trans-cinnamonitriles with olefins such as styrene and acrylonitrile were studied at 60°C. The copolymerization parameters of cinnamonitriles (M1) in the copolymerizations with styrene (M2) were determined to be r1 = 0,01 to 0,30, r2 = 0,45 to 4,25, Q1 = 0,06 to 0,70, and e1 = -0,52 to 1,35. The relative reactivity, log(1/r2), showed a tendency to increase with increasing Hammett constant σ and was higher in conjugated cinnamonitriles than in less conjugated nitriles. For p-substituted cinnamonitriles, ρ and γ values in the equation of log(1/r2) = ρ · σ + γ · ER were estimated to be 0,48 and 2,0, respectively, where ER is a resonance constant. The relative reactivity was also increased with increasing 13C NMR chemical shift of the olefinic β-carbon of cinnamonitriles and decreasing polarity of the solvents used. In addition, the relative reactivity towards a poly(acrylonitrile) radical is higher in cinnamonitrile than in cinnamic esters. The structure of the radical generated by the attack of the 2-methyl-2-propyl radical at the cinnamonitrile was examined by means of electron paramagnetic resonance (EPR) spectroscopy.
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/macp.1994.021950617
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