Synthesis of asymmetric star-branched polymers consisting of three or four different segments in composition by means of living anionic polymerization with a new dual-functionalized 1,1-bis(3-chloromethylphenyl)ethylene

A series of four-armed A₂BC, AB₂C, and ABC₂ asymmetric star-branched polymers with a three-component system, the A, B, and C segments of which are polystyrene, polyisoprene, and poly(4-trimethylsilylstyrene), respectively, have been successfully synthesized with a methodology based on living anionic polymerization with dual-functionalized 1,1-bis(3-chloromethylphenyl)ethylene ( 1 ). These star-branched polymers have well-defined architectures and precisely controlled chain lengths, as confirmed by size exclusion chromatography, ¹H and ¹³C NMR, vapor pressure osmometry, and static light scattering analyses. A simple and convenient one-pot process for star-branched polymer synthesis is an additional advantage of this methodology. One problem to be solved is that the synthetic route is limited in some cases by the inherently low reactivity of polyisoprenyllithium toward the 1,1-diphenylethylene functionality of in-chain-functionalized polymers. A new four-armed ABCD star-branched polymer, the A, B, C, and D segments of which are polyisoprene, poly(4-methoxystyrene), polystyrene, and poly(4-trimethylsilylstyrene), could also be synthesized through the extension of the methodology using 1 to a four-component system. The successful results strongly demonstrate the synthetic versatility and potential of this methodology for a wide variety of well-defined asymmetric star-branched polymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4535–4547, 2004