Photopolyaddition of dithiols to bis(alkoxyallene)s

Polyadditions of 1,4-benzenedithiol (BDT) to bis(alkoxyallene)s, such as 1,4-bis(allenyloxy)xylene (3) and 1,4-bis(allenyloxy) benzene (4) , were carried out in benzene at 25°C by irradiation with a high pressure mercury lamp. Thiol groups were added to the terminal double bonds of the allenyloxy groups selectively to afford polymers containing reactive carbon–carbon double bonds in the main chain, similar to the radical polyadditions using azobis(isobutyronitrile) (AIBN). The molecular weight of the polymer obtained from BDT and 3 was 10 times higher than that of the polymer produced in the radical polyaddition with AIBN; whereas the molecular weight of the polymer from BDT and 4 was similar to that in the radical polyaddition, probably because of poor solubility of 4 and the polymer toward benzene. The geometrical structure of carbon–carbon double bonds in the polymer isomerized from an E to Z structure with reaction time by virtue of both the addition elimination of thiyl radical to the double bonds and the UV irradiation. © 1996 John Wiley & Sons, Inc.     

Synthesis and cationic photopolymerization of alkoxyallene monomers

A series of cationically polymerizable mono-and difunctional alkoxyallene monomers have been prepared via the straight forward base catalyzed isomerization of the corresponding propargyl ethers. Rate studies conducted using real-time infrared spectroscopy showed that these monomers exhibit high reactivity in photoinitiated cationic polymerization. Monomers bearing a single alkoxyallene group undergo rapid polymerization to yield crosslinked polymers indicating that both double bonds react during polymerization. A mechanism has been proposed that explains this observation. © 1995 John Wiley & Sons, Inc.