Anionic polymerization: High vacuum techniques

Anionic polymerization is a powerful tool for the synthesis of a variety of model materials with well-defined molecular characteristics. However specially designed apparatuses and appropriate high vacuum techniques are needed in order to exclude from the reaction environment all reactive contaminants with the anionic centers. This review describes the basic principles of anionic polymerization as well as detailed experimental methods for the purification of the reagents usually used for the synthesis of model polymeric materials. In addition a few examples of the synthesis of polymers with complex architecture are given. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3211–3234, 2000

[1]  D. Worsfold,et al.  Anionic Polymerization of Isoprene , 1964 .

[2]  R. Quirk,et al.  Anionic polymerizations of non-polar monomers involving lithium , 1984 .

[3]  D. Worsfold,et al.  Developments in anionic polymerization — A critical review , 1988 .

[4]  T. L. Brown,et al.  Interaction of alkyllithium compounds with base , 1965 .

[5]  D. S. Pearson,et al.  Molecular characterization of poly(2-methyl-1,3-pentadiene) and its hydrogenated derivative, atactic polypropylene , 1985 .

[6]  J. Kennedy,et al.  Designed Polymers by Carbocationic Macromolecular Engineering: Theory and Practice , 1992 .

[7]  N. Hadjichristidis,et al.  Synthesis of Model 3-Miktoarm Star Terpolymers of Styrene, Isoprene, and Methyl Methacrylate , 1997 .

[8]  M. Szwarc |[lsquo]|Living|[rsquo]| Polymers , 1956 .

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

[10]  H. Lewis,et al.  Association of alkyllithium compounds in hydrocarbon media. Alkyllithium-base interactions , 1970 .

[11]  N. Hadjichristidis,et al.  MORPHOLOGY OF MIKTOARM STAR BLOCK COPOLYMERS OF STYRENE AND ISOPRENE , 1996 .

[12]  Paul von Ragué Schleyer,et al.  Sodium, Potassium, Rubidium, and Cesium: X-Ray Structurai Analysis of Their Organic Compounds1 , 1987 .

[13]  P. Dubois,et al.  Aluminium alkoxides: A family of versatile initiators for the ring‐opening polymerization of lactones and lactides , 1991 .

[14]  K. Hatada,et al.  Stereospecific polymerization of alpha-substituted acrylic acid esters polymerization , 1979 .

[15]  J. Mays,et al.  Linking reactions of living polymers with bromomethylbenzene derivatives: Synthesis and characterization of star homopolymers and graft copolymers with polyelectrolyte branches , 1999 .

[16]  I. Khan,et al.  Anionic ring opening polymerization of cyclotetrasiloxanes with large substituents , 1990 .

[17]  A. Hirao,et al.  Polymerization of monomers containing functional silyl groups. 11. Anionic living polymerization of 3-(tri-2-propoxysilyl)propyl methacrylate , 1992 .

[18]  K. Almdal,et al.  Aggregation in living polymer solutions by light and neutron scattering : a study of model ionomers , 1995 .

[19]  M. Delvaux,et al.  Star-branched polymers: 2. Linking reaction involving 2- and 4-vinyl pyridine and dienyland styryllithium chain ends , 1978 .

[20]  O. Webster Living Polymerization Methods , 1991, Science.

[21]  D. Margerison,et al.  The kinetics of the polymerization of styrene initiated by n-butyl lithium in hydrocarbon media , 1962, Proceedings of the Royal Society of London. Series A, Mathematical and physical sciences.

[22]  Apostolos Avgeropoulos,et al.  Synthesis of Model 16-Miktoarm (Vergina†) Star Copolymers of the A8B8 Type , 1996 .

[23]  L. Fetters,et al.  Synthesis and Properties of Block Polymers. I. Poly-α-methylstyrene-Polyisoprene-Poly-α-methylstyrene , 1969 .

[24]  R. West,et al.  The Physical Properties and Structure of t-Butyllithium , 1962 .

[25]  J. Jagur-grodzinski,et al.  Polybromostryl macromers and their anionic polymerization , 1983 .

[26]  J. Mays,et al.  Hydrodynamic properties of model 3-miktoarm star copolymers , 1995 .

[27]  R. Quirk,et al.  Anionic Polymerization: Principles and Practical Applications , 1996 .

[28]  J. Herz,et al.  Macromolecular engineering by anionic methods , 1988 .

[29]  R. Jerome,et al.  New developments in block polymerization , 1984 .

[30]  T. L. Brown Structures and reactivities of organolithium compounds , 1970 .

[31]  D. Pochan,et al.  Synthesis, Characterization, and Morphology of Model Graft Copolymers with Trifunctional Branch Points , 1996 .

[32]  M. Szwarc Living Polymers and Mechanisms of Anionic Polymerization , 1983 .

[33]  D. Worsfold,et al.  ANIONIC POLYMERIZATION OF STYRENE , 1960 .

[34]  M. Szwarc,et al.  POLYMERIZATION INITIATED BY ELECTRON TRANSFER TO MONOMER. A NEW METHOD OF FORMATION OF BLOCK POLYMERS1 , 1956 .

[35]  H. Dietrich Low temperature study of the structure of crystalline ethyllithium , 1981 .

[36]  S. Bywater,et al.  Preparation and Properties of Polydimethylsiloxane and Its Block Copolymers with Styrene , 1975 .

[37]  O. Okay,et al.  Anionic Dispersion Polymerization of 1,4-Divinylbenzene , 1990 .

[38]  J. Pople,et al.  Proposal for the mechanism of inversion of alkyl-lithiums , 1978 .

[39]  M. Möller,et al.  Poly(2-vinylpyridine) block copolymers. Phase separation and electric conductivity of iodine complexes† , 1989 .

[40]  D. Worsfold,et al.  Alkyllithium anionic polymerization initiators in hydrocarbon solvents , 1967 .

[41]  Toshimitsu Suzuki,et al.  Microstructure of Poly(2-phenylbutadiene) Prepared by Anionic Initiators , 1979 .

[42]  N. Hadjichristidis,et al.  Synthesis of a model 3-miktoarm star terpolymer , 1992 .

[43]  R. Jerome,et al.  Anionic polymerization of acrylic monomers. 6. Synthesis, characterization, and modification of poly(methyl methacrylate)-poly(tert-butyl acrylate) di- and triblock copolymers , 1991 .

[44]  K. Ute,et al.  Stereoregular polymerization of α-substituted acrylates , 1988 .

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

[46]  B. François,et al.  Kinetics of 1,3-cyclohexadiene polymerization initiated by organolithium compounds in a non-polar medium, 1. Pure propagation step , 1990 .

[47]  S. Bywater,et al.  The Polymerization of Isoprene with sec-Butyllithium in Hexane , 1968 .

[48]  P. Reed,et al.  The preparation and analysis of high purity organolithium initiators , 1972 .

[49]  W. Ritter,et al.  Strukturbestimmung eines 1,4‐poly(1,3‐pentadien)s durch 13C‐NMR‐spektroskopie , 1976 .

[50]  J. Vialle,et al.  Kinetics of polymerization of isoprene with butyllithium , 1968 .

[51]  P. Schleyer,et al.  Are Polar Organometallic Compounds “Carbanions”? The Gegenion Effect on Structure and Energies of Alkali‐Metal Compounds , 1994 .

[52]  J. Prud'homme,et al.  Microstructure of Poly(2,3-dimethyl-1,3-butadine) Prepared by Butyllithium in Cyclohexane. 220MHz Nuclear Magnetic Resonance Study , 1974 .

[53]  H. Mark,et al.  Encyclopedia of polymer science and engineering , 1985 .

[54]  M. Morton Anionic Polymerization: Principles and Practice , 1983 .

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

[56]  R. Datta,et al.  The bonding, structure and energetics of LiCH3, HBeCH3, HBeNH2 and their dimers: Ab initio molecular orbital calculations , 1973 .

[57]  N. D'Accorso,et al.  Stereoregular anionic polymerization of 2-isopropenylpyridine , 1983 .

[58]  Nikos Hadjichristidis,et al.  Synthesis and characterization of model 4-miktoarm star co- and quaterpolymers , 1993 .

[59]  M. J. O'brien,et al.  The synthesis, characterization, and deblocking of poly(4-tert-butoxystyrene) and poly(4-tert-butoxy-.alpha.-methylstyrene) , 1989 .

[60]  J. Mays Synthesis of “simple graft” poly(isoprene-g-styrene) by anionic polymerization , 1990 .

[61]  T. Long,et al.  Preparation of high purity, anionic polymerization grade alkyl methacrylate monomers , 1986 .

[62]  J. Alvariño,et al.  Polymerization kinetics of isoprene initiated by 1,1′-diphenyl-n-hexyl-lithium , 1972 .

[63]  T. L. Brown The Structures of Organolithium Compounds , 1966 .

[64]  H. Gilman,et al.  The Quantitative Analysis of Alkyllithium Compounds1 , 1944 .

[65]  H. Hsieh Kinetics of polymerization of butadiene, isoprene, and styrene with alkyllithiums. Part II. Rate of initiation , 1965 .

[66]  N. Scharnagl,et al.  Poly(lactones). 9. Polymerization mechanism of metal alkoxide initiated polymerizations of lactide and various lactones , 1988 .

[67]  B. François,et al.  Kinetics of 1,3‐cyclohexadiene polymerization initiated by organolithium compounds in a non‐polar medium, 2. Secondary reactions in the propagation step , 1990 .

[68]  W. Russel,et al.  Phase behavior and viscoelasticity of AOT microemulsions containing triblock copolymers , 1997 .

[69]  D. Margerison,et al.  Degrees of association of n-pentyl lithium and n-octyl lithium in benzene , 1971 .

[70]  R. Grubbs,et al.  Polymer synthesis and organotransition metal chemistry. , 1989, Science.

[71]  C. L. Lee,et al.  THE MECHANISM OF FORMATION OF LIVING α-METHYLSTYRENE DIMER AND TETRAMER , 1962 .

[72]  J. Mays,et al.  Nonlinear Block Copolymer Architectures , 1998 .

[73]  D. Bafus,et al.  The Infrared and Nuclear Magnetic Resonance Spectra of Ethyllithium , 1962 .