@article {8301, title = {Trifunctional organolithium initiator for living anionic polymerization in hydrocarbon solvents in the absence of polar additives}, journal = {Polymer Chemistry}, volume = {7}, year = {2016}, pages = {4090-4099}, abstract = {

A novel hydrocarbon-soluble trifunctional organolithium initiator, with no polar-additive requirements, has been synthesized for use in anionic polymerization. The complete synthesis of the unsaturated tri-diphenylethylene compound, 4,4,4-(ethane-1,1,1-triyl)tris(((3-(1-phenylvinyl)benzyl)oxy)benzene) (I), is described and the efficiency of the new initiator is evaluated using 1H NMR and Nano-assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry (NALDI-TOF MS). Activation of precursor I, was performed in situ using stoichiometric amounts of sec-BuLi in benzene. Three-arm polystyrene and polyisoprene stars with narrow molecular weight distributions were obtained in the case of relatively high total anion concentration, [sec-BuLi]0 \> 3.8 {\texttimes} 10-3 mol L-1 (3 {\texttimes} [I]0). At low total anion concentrations, uncontrolled molecular weight and broad/bimodal distributions were obtained, plausibly attributed to the presence of partially solvated aggregation dynamics complicating the propagation. The {\textquoteleft}living{\textquoteright} nature of the polymerization was confirmed by the sequential polymerization of styrene, and isoprene. The viscometric branching factor g{\textquoteright} values of the final branched polymers were measured and compared to g{\textquoteright} values of three-arm stars reported in the literature.

}, url = {http://0-pubs.rsc.org.pugwash.lib.warwick.ac.uk/en/content/articlelanding/2016/py/c6py00720a$\#$!divAbstract}, author = {George V. Theodosopoulos and Christopher M. Hurley and Jimmy W. Mays and Georgios Sakellariou and Durairaj Baskaran} }