By Maurice Morton
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1 •nd Monomers (continued) Initiator system Monomer 2-Isopropenylthiazole Double and Triple ft-BuLi, bulk; MgBr 2, toluene at 0° and 25°C ft-BuLi, bulk or hexane at 25°C BuLi or i-BuONa Remarks Re ferences Soluble polymers 451 Traces of polymer Oligomeric polypeptides 451 452 Low temperature ( —78°C); threo diisotactic configuration Transition polymerization occurred No termination High molecular weight Mixture of isotactic (32%), syndiotactic (13%), and heterotactic (55%) blocks The polymerization rate is slowed down by polymetha+ crylonitrile, water or ΜεΦ 3Ρ Ι~ ; reaction proceeds by a zwitterionic mechanism 453 BuLi in hexane and THF «-Butane formation and nitrile addition are important under these conditions 417 5-BuLi in benzene The nature of the active centers 458 Κ and Na α-methylstyrene oligomers, s-BuLi in THF at -70°C The active centers are able to attach to the cyano groups of some aromatic nitriles and to the carbonyl of benzophenone (added) 459 Et 3P in DMF Termination reaction by water 460 Et 3P Anionic zwitterion-type polymerization 461 N-Methyl-a-methylbeinzeneacrylamide rc-Butyllithium in toluene at 22° and -50°C Optically active polymer 462 2-Methyleneglutaroni trile Li naphthalene ( —35°C) or diphenylmethanelithium (-70°C) in DMF NaCN in DMF at -42 to -32°C Nearly white polymer (yield > 75%) with broad Μ WD and high degree of branching 463 Colorless polymer at low yield 464 Nitroethylene RNH 4-Vinyl- or 4-isopropenylthiazole Maleamide Mesaconamide Maleimides (N-substiltuted) Methacrylamide Methacrylonitrile «-BuLi in toluene and tetrahydrofuran 5-BuONa in polar solvents Lithium in NH 3 Sodium in NH 3 H-BuLi in toluene, — 78°C 40 Et 3P in THF 391 454 455 456 457 465 2-Nitrobutene 1-Nitropropene Phenylacetylene H-Butyllithium in DMSO; lithium in DMF and DMSO; LiAlH4 in tolu ene; NaH in DMSO; Na naphtha lene in THF; NaCN in DMF and CH2C12 Potassium bicarbonate BuLi in toluene, THF, or DMF MeONa tt-BuLi in heptane/(Me2N)3PO High conversions and low molecular weight polymer at 25°C; low temperatures (~ -78°C) may lead to the formation of high molecular weight material 466 High polymer Soluble amorphous polymer with MW ~ 38,000 Partly insoluble, with some degree of ordering Polymerization kinetics.
3,4-Hexatriene Double and Triple tt-BuLi BuLi in hexane, Et 3N, bulk, or THF C2D5-benzene-uf6 iso-BuLi in «-heptane Remarks References The influence of various parameters (temperature, solvent type, initiator concentration, pressure) upon the microstructure of polymer Kinetics of polymerization and microstructure NMR study of active chain ends A tough solid, insoluble in benzene, predominantly 1,4 configuration 326 327 9, 327a 328 32 Optically pure 2-methylbutyllithium Optically active polymer 249 Soluble VC13-A1(/-C4H9)3 High molecular weight, linear polymer; 1,2-, 1,4- and 1,6enchainment found; the trans-trans, the cis-trans, the conjugated and nonconjugated vinyl, and the trans groups found in 1,4- and 1,6-polyhexatriene Unsaturated reactive linear polymer of MW 1,000-7,000 prepared 329 BuLi in benzene at 0-30°C Isoprene •rid Monomers (continued) Na metals Li, Na, Cs, Rb metals, Li metal in hydrocarbons s-BuLi-diisopropenylbenzene drocarbon solvent BuLi in anisole in hy- H-BuLi in nonpolar and polar solvents Butylisoprenyllithium in ^-heptane and H-heptane-diethyl ether mixtures at 20°C High eis-1,4 content α,ω-Dilithiopolyisoprene of high eis-1,4 content was prepared The eis-1,4 content of the polymer decreased with increas ing pressure, apparently reflecting the augmented ionic character of the polymerization The microstructure of polymer prepared in hydrocarbon solvents is very sensitive to pressure, whereas in oxygenated solvents the structure remains unchanged Effect of ether on the rate of polymerization 330 331, 332 333 334-336 337 338 339 340 Tertiary N-substituted allylamines con taining Li 5-BuLi in «-hexane s-BuLi in hydrocarbon solvent at 30-45X 5-BuLi in cyclohexane «-BuLi in heptane EtLi, 5-BuLi in benzene, «-hexane and cyclohexane EtLi, s-BuLi in benzene s-BuLi in cyclohexane 5-BuLi or /-BuLi in benzene at 10°C BuLi in benzene 33 RLi/TMEDA Polystyryllithium, Na naphthalene, Na α-methylstyrene tetramer, or polystyrylsodium in THF at - 40 to 0°C Li diethylamide in hydrocarbon media and polar solvents Organoalkali metals in dioxane Li, Na, K, Cs catalysts in various solvents Graphite-alkali metals Polymers with functional groups prepared 341 The initiation step was studied.
3 Monomer Propylene oxide (continued) Heterocyclic Monomers (continued) Zn salts of xanthates, dithiocarbamates and thiocarboxylates i-BuN(EtZn) 2 + H 20 (trace) (bulk) f-Butyl oxirane /-BuOK or dimsylsodium at 30-60 C in Me2SO and Me2SOTHF mixtures Zn salts of xanthates, dithiocar bamates, and thiocarboxylate ZnEt 2-H 20 2,3-Dideuteromethyloxirane Trifluoromethyloxirane ZnEt 2-H 20, 65 C, bulk; ί-BuOK at 96 C /-BuOK in bulk or Zn(OCH 3) 2 in benzene (RO) 2Zn in benzene at 3 5 C KOH Epichlorohydrin Monosodium salt of hexafluoropentanediol NaOH 1,2-Butylene oxide 54 Optically active 2-methyl butylglycidyl ether Optically active methyl[ glyciidyl ether Isoamyl glycidyl ether Styrene oxide Remarks Initiator system KOH in hexane KOH Et 2Zn/H 20 or KOH MeOK at 80 C Potassium aromatic nitriles or ketones in THF (65-80 C) Re ferences High polymers 618 Isotactic polymer, addition of water enhances rate and also yield of isotactic Reaction mechanism 619 High polymers 618 Structural studies of the isotactic polymer by X-ray diffraction method Isotactic semicrystalline polymer; thermal transition study by DSC High yield; the MeOH-insoluble fraction has isotactic structure Stereochemistry of polymerization based on N M R Low MW polymer (970-4300) containing terminal unsaturation Polymer terminated with primary hydroxyl groups 621 620 622 623 624 625 625 Acetylene and hydrogep were generated through the polymerization The concentration of KOH did not affect the polymer yields Optically active polymer 626 Optically active polymer Chain transfer reaction involving the C — Η bond of the epoxide ring occurs Initiation mechanism depends both on the monomer and the metal complex used 629 630 627 628 631 Zn salts of xanthates, dithiocarbamates, thiocarboxylate High polymer 601 Et 2Zn-I 2 in THF Polymer was stabilized against oxidation by the ethylene sulfide-halogen adduct formed during polymerization reaction The polymer does not contain naphthalene or dihydronaphthalene groups in the chain Living polymer, kinetic study.
Anionic Polymerization: Principles and Practice by Maurice Morton