Potassium ion mediated living and controlled anionic polymerization of 2-vinylnaphthalene (2VN). Synthesis of P2VN-b-poly(alpha-methylstyrene) and P2VN-b-poly(9,9-dimethyl-2-vinylfluorene) block copolymers

The anionic polymerization is reported of 2-vinylnaphthalene (2VN) initiate d with potassium naphthalide (K-Naph), potassium 1,1,4,4,7,7,10,10-octameth yl-1,2,3,4,7,8,9,10-octahydronaphthacene (K-OMOHN), and alpha -methylstyryl dipotassium oligomers (AMS-K-2) in tetrahydrofuran at -78 degreesC. Narrow molecular weight distributions are obtained with good agreement of calculat ed and observed molecular weights. It is also possible to prepare poly(2-vi nylnaphthalene) (P2VN) of very high molecular weight (as high as 90 000) an d narrow polydispersity indices (PDI as low as 1.06). Under the above condi tions, the P2VN-K-2 has a shelf life exceeding 1 h as indicated by polymeri zation resumption experiments giving P2VN with statistical narrowing of the molecular weight distribution. The living character of the P2VN-K-2 dianio n was also demonstrated by the synthesis of narrow molecular weight distrib ution poly(alpha -methylstyrene)-b-P2VN-b-poly(alpha -methylstyrene), P2VN- b-poly(alpha -methylstyrene)-b-P2VN, and poly(9,9-dimethyl-2-vinylfluorene) -b-P2VN-b-poly(9,9-dimethyl-2-vinylfluorene) triblock copolymers and by qua ntitative end-functionalization with 1,4-bis(bromomethyl)benzene.