Synthesis and properties of new novolacs based on heteroatom-bridged phenol derivatives

Authors

  • Tadamasa Nemoto,

    1. Department of Organic and Polymeric Materials, Graduate School of Science and Engineering, Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo 152-8552, Japan
    Search for more papers by this author
  • Gen-Ichi Konishi

    Corresponding author
    1. Department of Organic and Polymeric Materials, Graduate School of Science and Engineering, Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo 152-8552, Japan
    • Department of Organic and Polymeric Materials, Graduate School of Science and Engineering, Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo 152-8552, Japan
    Search for more papers by this author

Abstract

We describe the synthesis and properties of new novolacs prepared by addition-condensation of heteroatom-bridged phenol derivatives and formaldehyde. The trifluoroacetic acid-catalyzed polymerization of equimolar amounts of bis(4-methoxyphenyl) ether (1a) and formaldehyde proceeded homogeneously to afford the polymer (2a) in 49% yield (Mn 2600, Mw/Mn 1.8). From the FTIR, 1H-NMR, and 13C-NMR spectra of 2a, it was evident that the polymer had methylene moieties-bridged repeating units in the polymer backbone. A higher molecular weight novolac (2a′) (yield 99%, Mn 16,600, Mw/Mn 12.9) could be prepared by using an excess of formaldehyde. Bis(4-methoxyphenyl) sulfone novolac (2b) (Mn 1300, Mw/Mn 1.2) and bis(4-methoxyphenyl) sulfide novolac (2d) (Mn 1200, Mw/Mn 1.9) were also prepared. However, the polymerization of bis(4-hydroxyphenyl) sulfone (1c) did not proceed, even when it was attempted under various reaction conditions. From TGA, the temperatures at 10% loss in weight (T10) for 2a, 2a′, and 2b were found to be 413, 430 and 393°C, respectively. These results suggested that heteroatom-bridged novolacs based on phenol derivatives have good thermal stability than other organosoluble polymers; moreover, these novolacs could be expected to function as processable materials, polymer blends for engineering plastics, etc. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Ancillary