Polymerizations, thermal butadiyne

In seeking new preparative routes to highly conjugated polymeric systems, we elected to investigate the polymerization of butadiyne. In this presentation we summarize previously unpublished work on a Ziegler-Natta polymerization of butadiyne and some of the more current developments on the thermal vapor deposition polymerization of this monomer. 

In several cases the >j -coordinated diyne ligand can be displaced by other ligands. The pentane-soluble, thermally stable compounds Ni(L2) (HC2C2H) (n= 1, 2 L2 = dippe, dippp) react with P(OPh)3 to give Ni P(OPh)3 4 with liberation of diyne and the bis-phosphine. The reaction of Ni(dippp) 2(/z-/ M- -HC2C2H) with four equivalents of CO resulted in polymerization of the butadiyne released from the metal center and the formation of Ni(CO)2(dippp). ... 

Butadiyne, H-CSC-C C-H, as a polymerizable monomer, has received very little attention from polymer chemists although its discovery dates back to Bayer in 1885. This structurally simple, highly reactive bifunctional molecule would be expected to have been a monomer of considerable interest in the field of polymer chemistry. Possibly, limited butadiyne stability may account for the small amount of polymerization research. The The compound is a liquified gas at room temperature (BP = 10 C), discolors slowly in sealed vessels at 20 C and may explode if heated. Storage and instability problems may be circumvented. Prevention of explosion may e accomplished by addition of an inert diluent such as butane. The monomer may also be stored in t e form of a labile complex with N-methyl-pyrrolidone. Its thermal condensation or polymerization was briefly recorded as an observation by Bayer and described in a little more detail by Miiller in 1925. Prevention of this thermal polymerization has been the subject of several patents with methylene blue, pyridine and vinylpyridine claimed as inhibitors. 

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