Synthesis of Cyclic Polystyrenes Using Living Anionic Polymerization and Metathesis Ring-Closure

A combination of living anionic polymerization and metathesis ring-closure provides an efficient method for synthesis of well-defined, macrocyclic polymers over a broad molecular weight range. A series of well-defined, α,ω-divinylpolystyrene precursors (Mn = 2800, 8600, 17000, and 38000 g/mol) were synthesized by 4-pentenyllithium-initiated polymerization of styrene followed by termination with 4-chloromethylstyrene. Efficient cyclization of these α,ω-divinylpolystyrene precursors was effected in CH2Cl2 and CH2Cl2/cyclohexane mixtures using a Grubb’s catalyst, bis(tricyclohexylphosphine)benzylidine ruthenium(IV) chloride. As the precursor Mn increased, more cyclohexane was added and the concentration of the precursor was decreased from 1.41 × 10–4 to 2.15 × 10–6 M. The macrocyclic polymers were uniquely characterized by MALDI–TOF mass spectrometry in terms of peaks that appeared characteristically 28 m/z units lower than those of the corresponding open-chain precursor peaks, corresponding to the loss of a...

[1]  M. Monteiro,et al.  Strategy for Rapid and High-Purity Monocyclic Polymers by CuAAC “Click” Reactions , 2010 .

[2]  M. Schulz,et al.  Macrocyclization of polymers via ring‐closing metathesis and azide/alkyne‐“click”‐reactions: An approach to cyclic polyisobutylenes , 2010 .

[3]  H. Kricheldorf.  Cyclic polymers: Synthetic strategies and physical properties , 2010 .

[4]  Scott M. Grayson,et al.  Synthesis and Degradation Behavior of Cyclic Poly(ε-caprolactone) , 2009 .

[5]  Scott M. Grayson,et al.  Synthetic approaches for the preparation of cyclic polymers. , 2009, Chemical Society reviews.

[6]  L. Ding,et al.  Cyclic poly(ε‐caprolactone) synthesized by combination of ring‐opening polymerization with ring‐closing metathesis, ring closing enyne metathesis, or “click” reaction , 2009 .

[7]  M. Schappacher,et al.  Naturally occurring and synthetic cyclic macromolecules , 2009, Cellular and Molecular Life Sciences.

[8]  D Richter,et al.  Unexpected power-law stress relaxation of entangled ring polymers. , 2008, Nature materials.

[9]  Scott M. Grayson,et al.  Efficient Preparation of Cyclic Poly(methyl acrylate)-block-poly(styrene) by Combination of Atom Transfer Radical Polymerization and Click Cyclization , 2008 .

[10]  K. Endo.  Synthesis and Properties of Cyclic Polymers , 2008 .

[11]  H. Oike.  Supramolecular approach for synthesis and functionalization of cyclic macromolecules , 2007 .

[12]  S. Hayashi,et al.  An efficient route to cyclic polymers by ATRP-RCM process , 2007 .

[13]  T. Hogen-esch.  Synthesis and characterization of macrocyclic vinyl aromatic polymers , 2006 .

[14]  Scott M. Grayson,et al.  An efficient route to well-defined macrocyclic polymers via "click" cyclization. , 2006, Journal of the American Chemical Society.

[15]  M. Arnould,et al.  Efficient Synthesis of ω-(p-Vinylbenzyl)polystyrene by Direct Functionalization of Poly(styryl)lithium with p-Vinylbenzyl Chloride in Hydrocarbon Solvent with Lithium 2,3-Dimethyl-3-pentoxide , 2006 .

[16]  K. Wagener,et al.  Recent advances in ADMET polymerization , 2005 .

[17]  R. Grubbs,et al.  Synthesis of cyclic polybutadiene via ring-opening metathesis polymerization: the importance of removing trace linear contaminants. , 2003, Journal of the American Chemical Society.

[18]  T. McLeish.  Polymers Without Beginning or End , 2002, Science.

[19]  R. Grubbs,et al.  An "Endless" Route to Cyclic Polymers , 2002, Science.

[20]  M. G. Finn,et al.  Click Chemistry: Diverse Chemical Function from a Few Good Reactions. , 2001, Angewandte Chemie.

[21]  H. Oike,et al.  Designing Unusual Polymer Topologies by Electrostatic Self-Assembly and Covalent Fixation , 2000 .

[22]  P. Butler,et al.  Effectiveχ and surface segregation in blends of star and linear polystyrene , 2000 .

[23]  G. Fredrickson,et al.  Effect of Architecture in the Surface Segregation of Polymer Blends , 1996 .

[24]  T. Hogen-esch,et al.  Formation of macrocyclic polymers by intramolecular coupling of α,ω‐difunctional precursors. Numerical evaluations , 1996 .

[25]  R. Quirk,et al.  Recent advances in anionic synthesis of functionalized elastomers using functionalized alkyllithium initiators. , 1996 .

[26]  A. Takano,et al.  Preparation of a Polystyrene Macromonomer with a Novel Anionic Initiator Containing an Olefinic Vinyl Group , 1994 .

[27]  R. Quirk,et al.  Dilithium initiators based on 1,3-bis(1-phenylethenyl)benzene. Tetrahydrofuran and lithium sec-butoxide effects , 1991 .

[28]  M. Szwarc.  Kinetics of reaction of living polymers with linking agents resulting in ring closure , 1989 .

[29]  J. A. Semlyen,et al.  Studies of cyclic and linear poly(dimethylsiloxanes): 28. Viscosities and densities of ring and chain poly(dimethylsiloxane) blends , 1988 .

[30]  G. Hadziioannou,et al.  Dilute solution characterization of cyclic polystyrene molecules and their zero-shear viscosity in the melt , 1987 .

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

[32]  H. Hanahata,et al.  Preparation of (p-vinylbenzyl)polystyrene macromer , 1983 .

[33]  L. Fetters,et al.  Anionic Polymerization of Vinyl Monomers , 1975 .

[34]  W. Glaze,et al.  Kinetics of Alkyllithium Initiated Polymerizations , 1970 .

[35]  F. Cartledge,et al.  The analysis of organolithium compounds , 1964 .

[36]  D. Grant,et al.  Carbon-13 Magnetic Resonance. II. Chemical Shift Data for the Alkanes , 1964 .

[37]  D. Worsfold,et al.  ANIONIC POLYMERIZATION OF STYRENE EFFECT OF TETRAHYDROFURAN , 1962 .

[38]  Homer Jacobson,et al.  Intramolecular Reaction in Polycondensations. I. The Theory of Linear Systems , 1950 .