The present work, we synthesized and polymerized 1,1'-naphthylbutadiene that has 4-carbon system. We tried to synthese the polymer of 4-carbon system that has a regio and stereo selectivity by radical polymerization introducing the bulky naphthyl group at 1-position of butadiene. Also, Zieglar-Natta polymerization was proceed to compare the polymer structure by polymerization method.
We failed to obtain high molecular weight (Mw) of poly(1,1'-naphthylbutadiene), (PolyNB), but only inherant viscosity of 0.1~0.2 in both polymerization method. Infrared spectra of polyNB were essentially the same regardless of the reaction method. 1,2-units were not founded in the polymers, as evidenced by the absence of the absorptions at 990 and $910 cm^{-1}$. The strong absorption at $965 cm^{-1}$ indicated that the double bonds in 1,4 and 3,4 units have mainly the trans configuration.
PolyNB-R showed more 1,4 content and PolyNB-ZN showed more 3,4 content in this study(220-MHz 1H NMR of PolyNB). The fraction of 1,4 and 3,4 units was estimated from relative intensities of the olefin proton resonance and checked by the methine proton resonances of 1,4 units at δ 3.5~4.5ppm.
We could completely hydrogenate the polyBD by p-toluenesulfonylhydrazide (PTSH) and could observe some iso-tacticity from this polymer, as evidenced by the singlet peak at 25.15 and 36,51 ppm $(^{13}CNMR)$.