Synthesis of polydiacetylenes from novel monomers having two diacetylene units linked by an arylene group

Three novel monomers 4BCMU4A(Ar) with chemical structures of R-C dropC-C dr opC-Ar-C dropC-C dropC-R, where R=-(CH2)(4)-OCONHCH2COOC4H9 and Ar=1,4-phen ylene (Ph or 2,3,5,6-tetrafluoro-1,4-phenylene (Ph) or 4,4'-biphenylene (Bi ph), were synthesized. 4BCMU4A(Ph) was found to be stable for solid-state p olymcrization, although 4BCMU4A(PhF) and 4BCMU4A(Biph) could be polymerized by W or gamma -ray irradiation. The polymerization for two polymerizable m onomers was investigated in detail mainly by solid-state C-13 NMR. The poly merization of 4BCMU4A(PhF) and 4BCMU4A(Biph) took place by 1,1-addition rea ction at one of the butadiyne moieties in the monomer to give single-chain- type polydiacetylenes with the respective butadiynylaryl moiety as a side c hain and ladder-type ones were not obtained. High crystallinity was confirm ed for these polymers by X-Ray diffraction. Polydiacetylene obtained from I BCMU4A(PhF) was found to be dispersed in organic solvent. Visible absorptio n spectra of this polymer in dispersion state with different compositions o f solvents and in amorphous state were investigated in comparison with the spectrum in the crystalline state.