Studies of Radical Alternating Copolymerization. I. Quantitative Determination of the Relative Reactivities between Free Comonomers and a Complex between Them; A Theoretical Treatment in Terms of Frontier Molecular Orbital Interactions. Application to Radical Maleic Anhydride-Vinyl Acetate Alternating Copolymerization
作者:
Roger Arnaud,
Claude Caze,
Jacques Fossey,
期刊:
Journal of Macromolecular Science: Part A - Chemistry
(Taylor Available online 1980)
卷期:
Volume 14,
issue 8
页码: 1269-1284
ISSN:0022-233X
年代: 1980
DOI:10.1080/00222338008056745
出版商: Taylor & Francis Group
数据来源: Taylor
摘要:
A simple quantitative determination of the ratio β1of rate constants kijcorresponding to the addition of a complex or a free monomer on a same growing chain in alternating copolymerization was determined. The application of this method to the case of alternating maleic anhydride (A)-vinyl acetate (D) copolymerization give for β1= kAC/kADand for β2= kDC/kDA(C refers to the complex) the respective values of 7 and 0. A complex was more reactive than A but less reactive than D toward a growing chain. In order to explain these reactivities, a frontier molecular orbital treatment was proposed. A good qualitative correlation with experimental results was obtained.
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