Synthesis of high‐molecular‐weight cyclic and multicyclic polystyrenes

Different cyclic architectures were prepared by combination of living anionic polymerization and coupling reactions. Well-defined macrocyclic polystyrenes were obtained by reaction of a two-ended living precursor dianion with an electrophile compound. Two types of coupling agent (diethylenic and dihalogeno compounds) were used and their influence on the cyclization yield was studied. Cyclization with a diethylenic product is preferred as it generates a macrocycle with two living centers and is able to react with a (multifunctional) nucleophile leading to more complex architecture. Cyclic polystyrenes with two attached linear branches were obtained by consecutive coupling of monofunctional and difunctional living chains with DDPE (1,3-bis(phenyl-ethylenyl)benzene). High molar mass multicyclic polystyrene was prepared by reaction of living macrocycles with poly(chloromethylstyrene). Size exclusion chromatography and matrix-assisted laser desorption ionization time of flight (MALDI-TOF) mass spectrometry analyses have confirmed the high efficiency of these coupling reactions. Copyright © 2003 John Wiley & Sons, Ltd.

[1]  H. Oike,et al.  Self‐Assembly and Covalent Fixation for Topological Polymer Chemistry , 2001 .

[2]  P. Hémery,et al.  Synthesis of multicyclic and grafted polystyrenes , 2001 .

[3]  M. Schappacher,et al.  α-Acetal-ω-bis(hydroxymethyl) Heterodifunctional Polystyrene: Synthesis, Characterization, and Investigation of Intramolecular End-to-End Ring Closure , 2001 .

[4]  H. Cramail,et al.  Synthesis and Characterization of Ring-Shaped Polystyrenes , 2000 .

[5]  C. Billaud,et al.  Synthesis, dimensions and solution properties of linear and macrocyclic poly(chloroethyl vinyl ether)‐g‐polystyrene comblike polymers , 1999 .

[6]  T. Itoh,et al.  Synthesis of α-Carboxyl, ω-Amino Heterodifunctional Polystyrene and Its Intramolecular Cyclization , 1997 .

[7]  D. Bertin,et al.  Controlled radical polymerization , 1996 .

[8]  K. Ishizu,et al.  Novel synthesis and characterization of cyclic polystyrenes , 1996 .

[9]  Jingjing Ma.  Synthesis of well‐defined macrocyclic block copolymers using living coupling agent method , 1995 .

[10]  Bumjae Lee,et al.  Anionic Synthesis of Heteroarm, Star-Branched Polymers. Scope and Limitations , 1994 .

[11]  R. Yin,et al.  Synthesis and characterization of narrow-molecular-weight-distribution polystyrene-poly(dimethylsiloxane) macrocyclic block copolymers and their isobaric precursors , 1993 .

[12]  R. Quirk,et al.  Anionic synthesis of ω-1,1-diphenylethylene-terminated polystyrene macromonomers. Rational synthesis of ABC hetero three-armed-star-branched polymers , 1993 .

[13]  P. Hémery,et al.  Synthesis of ring‐shaped polyisoprene , 1992 .

[14]  T. Hogen-esch,et al.  Synthesis and characterization of topologically interesting vinyl polymers , 1991 .

[15]  J. Roovers.  Viscoelastic properties of polybutadiene rings , 1988 .

[16]  M. Antonietti,et al.  Synthesis and characterization of “eight‐shaped” polystyrene , 1988 .

[17]  P. Sigwalt,et al.  New perfectly difunctional organolithium initiators for block copolymer synthesis: 3. Kinetics of addition of tert-butyllithium on 1,2-bis(isopropenyl-4 phenyl)ethane , 1987 .

[18]  G. McKenna,et al.  Solution properties of ring-shaped polystyrenes , 1986 .

[19]  J. Roovers,et al.  Synthesis of high molecular weight ring polystyrenes , 1983 .

[20]  H. Höcker,et al.  1,3‐Bis(1‐phenylvinyl)benzene and its reactions with electron transfer reagents , 1977 .

[21]  J. A. Semlyen.  Ring-chain equilibria and the conformations of polymer chains , 1976 .