Reactions of polystyryl anions with carbon dioxide and oxygen. Analysis of products by silica gel chromatography

Abstract

Polystyryllithium was prepared by anionic polymerization. This “living polymer” and the polystyrylmagnesium bromide derived from it were treated with carbon dioxide (solid or gas). The highest yields of carboxylic acid were obtained when solid carbon dioxide was used with polystyryllithium or by treatment of polystyrylmagnesium bromide with gaseous carbon dioxide. The products from the reaction of polystyryllithium with oxygen were polymeric ketone X, the alcohols IXa and IXb, and coupling products (e. g., XI). The various functionalized and unfunctionalized polystyrene products were isolated by chromatography on silica gel and were characterized by gel permeation chromatography (GPC), thin layer chromatography (TLC), and high‐performance liquid chromatography (HPLC) in combination with chemical transformations.

Kinetics of the anionic polymerization of 2-(tertbutyldimethylsilyloxy) ethyl methacrylate

“…This indicates a coupling reaction. Oxidative coupling has been observed for nonpolar monomers when the quenching agent was not degassed [19]. However, enolates have not been observed to undergo this reaction.…”

Supramolecular Materials from Triblock Rodcoil Molecules Containing Phenylene Vinylene

“…The reaction was stirred for 30 min. Isoprene (4.37 mL, 43.7 mmol, 9.0 equiv) was added, the reaction stirred for an additional 30 min, and was then quenched by bubbling dry CO 2 through the solution followed by 3 mL of 6 N HCl/THF (1/5). , The solvent was removed by rotatory evaporation. The crude material was loaded onto 300 mL of silica gel using CH 2 Cl 2 as the solvent.…”

Synthesis of carboxy‐terminated telechelic oligostyrenes by Dead End Polymerization

“…In this paper, the synthesis of carboxy‐telechelic oligostyrene is studied with M n about 2000 g mol −1 . Several methods can lead to carboxy‐telechelic polystyrene (CTPS) 19–23. Carboxy‐terminated polystyrene can be prepared by end‐capping the polystyrene living anion with carbon dioxide.…”

“…Carboxy‐terminated polystyrene can be prepared by end‐capping the polystyrene living anion with carbon dioxide. Mansson19 developed this method and mentions the appearance of by‐products such as dipolystyrylketone or tripolystyrylmethanol. He used chromatography on silica gel medium for the separation of functionalized polystyrenes, which are eluted in a methylcyclohexane/THF mixture.…”