Phenylacetylene anionic polymerization

To be eligible to living anionic polymerization a vinylic monomer should carry an electron attracting substituent to induce polarization of the unsaturation. But it should contain neither acidic hydrogen, nor strongly electrophilic function which could induce deactivation or side reactions. Typical examples of such monomers are p-aminostyrene, acrylic esters, chloroprene, hydroxyethyl methacrylate (HEMA), phenylacetylene, and many others. 

Anionic polymerization of phenylacetylene to a trans-cisoid polymer in the presence of crown ether phase-transfer catalysts initiated by sodium amide has been reported.425 In contrast, the zwitterionic rhodium complex Rh+(COD)BPhJ yields a ds-transoid product in the presence of Et3SiH.426... 

The loss of the addition ability of an ion by delocalization of the electron defect in a conjugated polyene chain is documented by the observation of Subramanian et al. They polymerized monomers with C=C and C=N bonds by electroinitiation. Anionic polymerization of phenylacetylene started very easily but it rapidly died out without any external cause [109]. The polymerization of n-alkyl-2-cyanoacrylatet in the presence of tetracyanoethy-lene yields only low-molecular-weight products. This is due to the formation... 

Silylene 1 is an unusually versatile catalyst for alkene and alkyne polymerization. The list of compounds polymerized by 1 includes ethene, propene, 1-hexene, styrene, dimethylbutadiene, vinylidene chloride, vinyl ethyl ether, methyl methacrylate, and phenylacetylene. The polymerization does not seem to take place by any of the usual mechanisms, anionic, cationic or free-radical. Instead it somewhat resembles coordination polymerization, as observed for Ziegler-Natta type catalysts. Silylene 2 also catalyzes the polymerization of 1-hexene, but the polymerization is 10 to 100 times slower than with 1. 

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