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Studies on Polymerization of Vinyl Compounds Initiated by Metal Chelate II Kinetics of Polymerization of Methyl Methacrylate Initiated by Nickel Ethyl Acetoacetate in the Presence and the Absence of Aromatic Amines
Author(s) -
Chen ChihTsung,
Lin PiChou,
Huang YunKuang,
Shiau ChuanLiang
Publication year - 1970
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.197000021
Subject(s) - chemistry , aniline , polymerization , monomer , polymer chemistry , methyl methacrylate , ethyl acetoacetate , chelation , nickel , polymer , inorganic chemistry , organic chemistry , catalysis
The kintetic studies of polymerization of methyl methacrylate initiated with nickel ethyl acetoacetate gave the following equations. R p =K 1 [Monomer] 1.4 [Chelate] 0.5 , in the absence ox aniline R p =K 2 [Monomer] 1.2 [Chelate] 0.5 [Aniline] 0,5 , in the presence of aniline. Some aromatic amines such as aniline markedly accelerated the polymerization, while pyridine had no such effect. The activation energy of initiation was 24.8 kcal / mol in the absence of aniline, and 8.8 kcal / mol in the presence of aniline. Both the kinetic data and the infrared spectra of the polymer indicated that the polymerization was radical in nature. The reaction order against monomer varied, as the temperature differed. The spectrophotometric investigation indicated formation of a complex between the chelate and the monomer, or amines. It also showed that the formation of a complex was not a factor which controlled the rate of initiation. A scheme of initiation mechanism was presented on the basis of the above experimental evidence.