Synthesis of Functional Polyphenylenes from Substituted Hydroquinones via Nickel(0)-Catalyzed Polymerization of Their Bismesylates

Abstract

This paper reports the elaboration of a novel synthetic method for the preparation of polyphenylenes. It consists of the Ni(0)-catalyzed polymerization of bis[(methylsulfonyl)oxy] derivatives (i.e., arylene bismesylates) of substituted hydroquinones. The Ni(0) catalysts used were generated in situ from NiCMPPhsh, Zn, Et*NI in THE, dioxane, or DMAc. The influence of solvent, temperature, additional ligands, and the size and electronic properties of the substituent groups of the monomers on their polymerizability was investigated. Soluble poly(p-phenylene)s and poly(m-phenylene)s can be obtained by a proper selection of their substituents. Poly(p-phenylene)s with number-average molecular weights (relative to polystyrene standards) of up to 20 030 (DP = 101) were obtained.

Poly(p-phenylene alkylene)s – A forgotten class of polymers

“…For example, Ueda et al synthesized aromatic poly(ether ketone)s 81) . Other examples include work by Kantor et al who used the Kumada coupling for the preparation of main-chain liquid-crystalline polymers based on a biphenyl moiety 34,35) , and Percec et al who described aryl sulfonates undergoing Ni(0)-catalyzed homocoupling resulting poly(p-phenylene)s 82) . However, the molecular weights the latter two groups obtained were rather limited (M -n l 2 000 -7 000), in part due to the precipitation of the growing polymers from the polymerization solvent.…”

Synthesis of high performance polyacrylonitrile by RASA SET-LRP in the presence of Mg powder

“…[38][39][40][41][42][43][44][45][46][47][48] In ARGET ATRP, various reducing agents (RAs) including zero valent copper, zinc, magnesium, iron, and ascorbic acid are used to reduce transition metal complex in a high oxidation state to in a low oxidation state. [49][50][51][52] SET-LRP of methyl methacrylate catalyzed by in situ prepared Cu(0) at ambient temperature using various metallic powders including Zn(0), Ni(0), Mg(0), and Fe(0) was attempted.…”

Synthesis of Conducting Organic Polymeric Materials Mediated by Metals: How the Organic Chemists Make Some of the Most Advanced Polymeric Materials

“…Poly(p-phenylene)s have been prepared in a similar way using easily available dihydroquinones as starting materials. The process starts with the transformation of the dihydroquinones to the triflate [107] or mesylate [108] derivatives 78 (Fig. (21)).…”