ISSN:
0025-116X
Keywords:
Chemistry
;
Polymer and Materials Science
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
The copolymerization of N-cyclohexylmaleimide (1) (M1) and bis(2-ethylhexyl) itaconate (2) (M2) with dimethyl 2,2′-azoisobutyrate (3) as an initiator was carried out at 50°C in benzene. Monomer reactivity ratios were estimated as r1 = 0,34 and r2 = 0,38. The copolymerization rate (Rp) and the molecular weight of the resulting copolymer increased with increasing concentration of 1 when the total concentration of comonomers was fixed at 1,00 mol. L-1. Rp was proportional to [3]0,5, indicating a usual bimolecular termination in the copolymerization. An electron spin resonance (ESR) spectrum of the propagating polymer radicals was observable in the actual copolymerization system at 50°C. The spectrum of the copolymerization system is inexplicable in terms of any superposition of spectra observed in the corresponding homopolymerization systems, revealing that some penultimate monomeric unit causes a change in the ESR spectrum, that is, the structure of propagating polymer radical. The apparent rate constant of propagation (kp) and termination (kt) were estimated by ESR. The kp values (1,5-50 L · mol-1 · s-1) are fairly higher than those estimated on the basis of the terminal model, affording another piece of evidence for the penultimate effect. The kt value (1,8-5,4·103 L · mol-1 · s-1) shows a behaviour similar to that of the intrinsic viscosity of the resulting copolymer on varying the monomer feed composition, which seems to reflect diffusion-control of termination reactions.
Additional Material:
9 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/macp.1993.021940809
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