Detail of "14804-38-7"

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Mechanistic studies on the oxidative coupling polymerization of phenols

Mechanistic studies on the oxidative coupling polymerization of phenols. VI. Comparison of reactivities of 2,6-dimethylphenol, poly(phenylene oxide)-dimer, and -trimer in the copper-catalyzed oxidative coupling polymerization. Viersen, F. J.; Renkema, J.; Challa, G.; Reedijk, J. (Lab. Polym. Chem., State Univ. Groningen, Groningen 9747 AG, Neth.). J. Polym. Sci., Part A: Polym. Chem., 30(5), 901-11 (English) 1992. CODEN: JPACEC. ISSN: 0887-624X. DOCUMENT TYPE: Journal CA Section: 35 (Chemistry of Synthetic High Polymers) In the oxidative coupling polymn. catalyzed by Cu-amine complexes, the oxidn. rates of 2,6-dimethylphenol (I) and its C-O-coupled dimer [4-(2',6'-dimethylphenoxy)-2,6-dimethylphenol], and trimer [4-(-4'-(2'',6''-dimethylphenoxy)-2',6'-dimethylphenoxy)-2',6'-dimethylphe noxy))-2,6-dimethylphenol] were detd. 7447-39-4 and 14804-38-7 which are cas registry numbers are also used here. The I concn. dependence showed a Michaelis-Menten-type behavior. On the other hand, the dimer and trimer showed a 1st-order rate-dependence in the resp. phenol concns. The slow reaction step following an equil. complex formation between I and Cu complex was relatively fast for both the dimer and the trimer. Therefore, coordination of dimer or trimer to the Cu complex was rate-detg. Furthermore, the dimer and trimer gave overall reaction rates ~8 times higher than found for I. Following the Flory principle of equal reactivity for functional groups of oligomers in polycondensations, all polyoxyphenylene oligomers had equally high oxidn. rates as the dimer and trimer. The yield of undesired diphenoquinone (II) side product was strongly reduced when starting with the dimer (0.18%), or trimer (0.17%), compared to 3.3% for I. This is not unexpected, since II was only formed from 2 monomeric I residues. Using a 1:10 M mixt. of dimer-I already resulted in a II yield of only 1.7%. Furthermore, when starting from I, II was predominantly formed during the 1st 30% conversion. Starting from dimer (or trimer), II was formed at an almost const. very low rate during the whole course of the reaction. The most important polymn. reaction involved oxidn. of Cu-coordinated I anion to its corresponding cations, followed by coupling with a Cu-coordinated polyoxyphenylene chain. .