Ethynyl‐terminated polysulfones and ethynyl‐terminated polyether‐ketones were prepared in a one‐step polyetherification reaction using new end‐capping agents, respectively 4‐ethynyl‐3′‐nitrodiphenylsulfone and 4‐ethynyl‐4′‐nitrobenzophenone. These reagents were prepared according to a three‐step route each. End‐capping of the polymers involve the nitro displacement by a phenoxide ion. The nitro group was found to be more reactive than the fluoro one as a leaving group. Due to the thermally induced reaction of their ethynyl end‐groups, the polymers lead to materials with improved glass transition temperatures and good thermostability.

SynopsisDifferent main chain acetylene terminated polyethers with various molecular weights were prepared in a one-step polyetherification reaction. This process requires the synthesis of new acetylene end-capping agents, 4-ethynyl-4'-fluorobenzophenone and 4-ethynyl-4'-fluorodiphenyl sulfone. These reagents were prepared with good yields in a three-step route. The thermally induced reaction of the ethynyl groups in an easy process leads to materials with improved solvent resistance and good thermostability. The fracture toughness was evaluated and was found to increase with the molecular weight of the precursor oligomers. High values were obtained, especially when 4,4'benzophenone and 4,4'-diphenyl sulfone units are present in the polymer main chain.

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