Reaction of polystyryllithium with carbon dioxide

Abstract

A benzene solution of polystyryllithium of narrow chain length distribution was found to react with carbon dioxide to form (upon acidification) not only the corresponding polystyrene carboxylic acid but also significant amounts of di‐polystyryl ketone and tri‐polystyryl carbinol. The amounts of the latter two products were somewhat dependent on the rate at which carbon dioxide could be added to the system. Thus, the yields of di‐polystyryl ketone and tri‐polystyryl carbinol were 28% and 12% respectively, if termination was accomplished by allowing gaseous carbon dioxide to diffuse into the system, but the total yield of these products was only 22% if the termination was carried out by pouring the polystyryllithium solution onto crushed, solid Dry Ice. Lithium polystyrene carboxylate was found to be partly associated in benzene and cyclohexane, but the free acid was not.

Aziridine Termination of Living Anionic Polymerization

“…epoxide polymerization, is suppressed when lithium is used as a counterion . Other possibilities include the reaction with carbon dioxide to carboxylic acid end groups and the use of 1,1 ‐diphenylethylene derivatives to yield various end groups . The introduction of amine groups is commonly more complicated and needs more than one reaction step .…”

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.…”

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

“…e.g., ref. 2), presumably were present in the materials eluted first in the above-mentioned column chromatography of the crude reaction products. This by-product material (gaseous carbon dioxide used in the reaction with polystyryllithium) was subjected to analytical study.…”

“…Thin layer chromatograms (silica gel) of(1) crude product from treatment of polystyryllithium (R,, = 2500) with gaseous carbon dioxide,(2) crude product from treatment of polystyryllithium (a,, = 18,000) with solid carbon dioxide,(3) product from treatment of polystyryllithium (M,, = 2500) with degassed methanol. Solvents: (A) light petroleum/dichloromethane (3:7), (B) dichloromethane, (C) diethyl ether.ponents(Fig.…”