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The cumulene 1,1,4,4-bis(pentamethylene)butatriene has been shown to undergo a thermally induced 1,4 free-radical polymerization to yield a crystalline polymer with a unique nonconjugated acetylene containing backbone. This polymerization occurs in both the melt and in solution. Typical free-radical inhibitors prevent the thermally induced polymerization. The reaction occurs in the presence or absence of free-radical initiators. The polymer is crystalline with a triclinic unit cell (a ) 9.87 Å, b ) 6.10 Å, c ) 4.97 Å, R ) 113.7°, ) 85.2°, γ ) 100.6°). No melting or glass transition is observed via differential calorimetry, but an irreversible exothermic transition is observed from both solution and melt polymerized material. This is interpreted as a cold crystallization process. Trapping of the polymerizing monomer with TEMPO leads to soluble oligomers. † This paper is dedicated to Professor Shelton Bank on the occasion of his 65th birthday.

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