Novel polyacetylenes, poly(1) and poly(2) substituted with benzoxazine rings were synthesized by the polymerization of the corresponding acetylene monomers 1 and 2 using Rh catalysts, [(nbd)RhCl]2, and (nbd)Rh+B–Ph4 (nbd = 2,5‐norbornadiene). The polymers were heated at 250 °C under N2 to obtain the corresponding polybenzoxazine resins, poly(1)′ and poly(2)′ possessing polyacetylene main chains via the ring‐opening polymerization of the benzoxazine moieties. The polyacetylene backbones were maintained after crosslinking reaction at 250 °C, which were confirmed by Raman spectroscopy. The benzoxazine resins were thermally highly stable as evidenced by differential scanning calorimetry and thermogravimetric analysis. The surface of poly(1)′ film became hydrophilic compared to that of poly(1), while the surfaces of poly(2) and poly(2)′ films showed almost the same hydrophilicity judging from the water contact angle measurement. Poly(1)′ and poly(2)′ exhibited refractive indices smaller than those of poly(1) and poly(2). © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 1884–1893

The Sonogashira–Hagihara coupling polymerization of ferrocene‐containing l‐phenylalanine‐derived optically active o‐, m‐, p‐substituted bis(iodophenylene) monomers 1o , 1m , 1p with 1,4‐diethynylbenzene (2) and 1,4‐diethynyl‐2,5‐bis[2‐(2‐methoxyethoxy)ethoxy]benzene (3) is carried out to obtain the corresponding polymers consisting of ferrocene, amino acid, and phenyleneethynylene moieties. In the solution state, poly(1o ‐2), poly(1o‐3), and poly(1m ‐2) exhibit no circular dichroism (CD) signals in N,N‐dimethylformamide (DMF), while poly(1m‐3), poly(1p ‐2), and poly(1p ‐3) exhibit CD signals assignable to the main chain chromophore, indicating the formation of certain chiral structures. In the solid state, poly(1o ‐2), poly(1o‐3), poly(1m ‐2), and poly(1m‐3) exhibit CD signals in the solid state, while poly(1p ‐2), poly(1p ‐3) does not, indicating the different aggregation manners of the polymers in the solution and solid states. The monomer and the polymers exhibit redox properties assignable to the ferrocene moieties. Thermal gravimetry analysis (TGA) measurements reveal that a 30% weight reduction occurs at 500 °C yielding black ferromagnetic solids.