Synthesis of Polydiacetylenes with Pyridyl Groups Directly Bound to the Main Chain

Abstract

N-Substituted carbamic acid esters of 8-pyridyl-5,7-octadiyn-1-ol were synthesized and all the monomers showed solid-state polymerizabilities by UV irradiation to give polydiacetylenes with pyridyl groups directly bound to the π-conjugated backbone. Hydrogen-bond complexes of these monomers with dodecanoic acid (DA) or perfluorododecanoic acid (PFDA), in which the pyridyl nitrogen atom formed a hydrogen bond with the hydrogen atom of the carboxyl group, were also prepared. Although complex formability of DA with the monomers in this study was not so high, many PFDA complexes were obtained because of the higher acidity. All complexes could be polymerized in the solid state and the conversion increased by complexation compared with the original monomers. More favorable monomer stacking for solid-state polymerization could be achieved by combination of intermolecular hydrogen bonds between urethane groups and alkyl (or perfluoroalkyl) chain packing.

Keywords:

• Solid-state polymerization
• conjugated polymer
• polydiacetylene
• pyridyl group
• hydrogen-bond complex

Acknowledgment

This work was supported by a Grant-in-Aid for Scientific Research on Priority Areas (No. 17067001) from the Ministry of Education, Culture, Sports, Science and Technology and a Grant-in-Aid for Challenging Exploratory Research (No. 21655048) from Japan Society for the Promotion of Science.