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The preparation and characterization of high‐molecular weight diphenyl oxide‐ and Diphenyl sulfide (cas 139-66-2)‐novolacs are described. The polymerization of diphenyl oxide with 2 equivalence of formaldehyde proceeded to give the corresponding polymer (2) (Mn: 160,000, Mw/Mn: 29.1) in good yield. Further, an ultra high‐molecular weight fraction (Mw > 1,000,000) was observed in the GPC trace of 2. The developed polymers can be considered as a new class of aromatic polymers that exhibit both novolac‐like and engineering plastic properties and are thus promising compounds for material‐engineering applications. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010
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