Oxidative coupling polymerization of 2,3‐dihydroxynaphthalene with dinuclear‐type copper(II) catalyst

Abstract

The oxidative coupling polymerization of 2,3‐dihydroxynaphthalene with the novel dinuclear‐type copper(II) catalysts successfully produced poly(2,3‐dihydroxy‐1,4‐naphthylene). For example, the MeOH‐insoluble polymer with a number average molecular weight of 4.4 × 103 from the polymerization using the complex of CuCl2 and N,N′‐bis(2‐morpholinoethyl)‐p‐xylylenediamine (p‐1) at room temperature under an O2 atmosphere followed by acetylation of the hydroxyl groups was obtained in 63% yield. The structures of the tetraamine ligands and the counter anion of the copper(II) salts significantly influenced the catalyst activity. The polymerization of 2,2′‐dimethoxy‐1,1′‐binaphthalene‐3,3′‐diol with the 2CuCl2‐p‐1 catalyst, however, resulted in a lower yield. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1635–1640, 2005

Monomer/polymer Schiff base copper(II) complexes for catalytic oxidative polymerization of 2,2′‐dihydroxybiphenyl

“…Many catalytic systems have been used to obtain these polymers such as enzymes, Schiff base complexes of Fe(III) and Cu(II) as well as transition metal salts of Fe, Cu, Co, and so forth 7–9. Habaue et al studied oxidative polymerization of 2,3‐dihydroxynaphthalene using Copper(II) and catalysts 10. Ueda and coworkers studied regiocontrolled synthesis of poly(2,6‐dihydroxy‐1,5‐naphthylene) with high molecular weights by oxidative coupling polymerization 11.…”

Oxidative Coupling Polymerization of 2,6-Dihydroxynaphthalene in Basic Water

“…6 Habaue et al recently prepared also the non chiral polymer by the direct oxidative coupling of 2,3-DHN. 7 On the course of exploring the polymerization system to prepare stereoregular PDHN, we noticed the recent articles by Nishide et al about the oxidative coupling polymerization of 2,6-dimethylphenol in water. 8 We have already found that PDHN, as well as 2,6-DHN, is soluble in basic water and can be used as alkaline-developable photo-resist.…”

New asymmetric vanadium catalyst for highly selective oxidative coupling polymerization

“…1). 7, 25 The polymerizations with the VOSO 4 –diamine complexes, such as (+)PMP and (−)Sp, resulted in no product and a poor yield (runs 1 and 2). The polymerization conditions, such as the [VOSO 4 ]/[Phbox] ratio (1/2) and polymerization temperature (0 °C), affected the catalyst performance and reduced the polymer yield with a rise in the specific rotation value (runs 5 and 6).…”