By Maurice Morton
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Extra resources for Anionic Polymerization: Principles and Practice
Polymerization rate was slowed in the presence of sodium tetraphenylboride Living polymers, kinetic study 632 636 637 Na naphthalene in THF at —70° and 0°C Thiolate group association Optically active monomer gave optically active poly(propylene sulfide) The polymer does not contain naphthalene or dihydronaphthalene group in the chain (cf. , were used as promoters 658 LiH, LiNH 2 A promoter is forr ned in situ by the reaction of 200-1400 ppm water in trle monomer with sufficient isocyanate to reduce water content to < 50 ppm 659 NaH, NaOMe at 145-175°C l-Chloro-3-oxoiso indolenine as a promoter 660 Na caprolactam salt at 120°C 661 ( NCN02 as polymerization accelerator.
1 Monomer 1 - Vinylanthracene 2-Vinylanthracene (and 2-propenyl-2-anthracene) 9-Vinylanthracene 42 Vinyl aryl monomers CH2 = CH(R)C 6H 4R' (11 monomers) /7-Vinylbenzamide Vinyl chloride Double and Triple ond Monomers (continued) Remarks Initiator system Na α-methylstyrene tetramer in THF (-78°C) Na α-methylstyrene tetramer (THF), -78°C BuLi (benzene) Na naphthalene, Ν a biphenyl Na biphenyl, Na naphthalene, BuLi, Na α-methylstyrene tetramer, living polystyrene in THF or benzene at -78 to +25°C Na naphthalene, Na benzalaniline, H-BuLi in THF 5 Soluble polymer, MW ~ 10 478 High polymer of broad Μ WD 478 Oligomer Oligomers Some give crosslinked polymers, but most give linear polymers.
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.
Anionic Polymerization: Principles and Practice by Maurice Morton