Synthesis of hydrogen‐terminated aliphatic bis(ethynyl ketone)s and aliphatic poly(enamine‐ketone)s and poly(enonesulfide)s

Abstract

Abstract Hydrogen‐terminated aliphatic bis(ethynyl ketone)s (H‐ABEKs): 1,9‐decadiyne‐3,8‐dione ( 3a ) and 1,13‐tetradecadiyne‐3,12‐dione ( 3b ) were prepared by the Friedel‐Crafts reaction of bis(trimethylsilyl) acetylene (BTMSA) with adipoyl chloride and sebacoyl chloride, followed by desilylation with an aqueous buffer solution. Aliphatic poly(enamine‐ketone)s (APEKs) and aliphatic poly(enonesulfide)s (APESs) were prepared in nearly quantitative yield by the nucleophilic addition polymerization of 3a,b with various diamines and dithiols in N,N ‐dimethylformamide (DMF) and m ‐cresol at room temperature during 14‐22 h. Aromatic diamines and dithiols gave polymers that were soluble only in m ‐cresol. Primary diamines gave exclusively APEKs with the cis (Z) configuration. Dithiols gave APESs which contained more cis (Z) than trans (E) configurations. The inherent viscosities (η inh ) of the APEKs ranged from 0.05 to 0.73 dL/g. The APESs gave η inh ranging from 0.36 to 2.21 dL/g.