Preparation of (p-Isopropenylphenethyl) poly (α-methylstyrene) Macromonomer and Anionic Polymerization of the Macromonomer

• Published in: KOBUNSHI RONBUNSHU 1992/10/25, Vol.49(10), pp.817-823
• Main Authors: SE, Kazunori, SUZUKI, Masaaki, MATSUO, Togoroh, UMEDA, Tatsuo, UENO, Masanobu
• Format: Article
• Language: Japanese
• Subjects: Anionic Polymerization; Ceiling Temperature; Coupling Efficiency; Coupling Reaction; Low-Angle Laser-Light-Scattering; p-Isopropenyl-phenethyl Chloride; Poly (α-methylstyrene) Macromonomer; Tetrameric Sodium-Dianions of α-Methylstyrene; Vapor Pressure Osmometer
• ISSN: 0386-2186; 1881-5685
• DOI: 10.1295/koron.49.817

In order to prepare (p-isopropenylphenethyl) poly (α-methylstyrene) macromonomer, the direct coupling reaction of poly (α-methylstyryllithium) with p-isopropenylphenethyl chloride was carried out in THF at -78°C under 10-6 mmHg. The molecular characteristics were measured with GPC, vapor pressure osmometer, NMR, and low-angle laser-light-scattering. Three macromonomers were obtained in the Mn range of 2000 and 7100; the Mw/Mn values were 1.09-1.12. The coupling efficiencies are 0.98-1.00. When the macromonomer solution was added to the sodium mirror, the solution color changed to red. The ultraviolet spectra and NMR spectra of the solutions were measured under vacuum; the GPC chromatograms of the precursors were also measured. The isopropenylphenethyl group whose ceiling temperature was less than room temperature, reacted with the sodium to give not the dimetric and/or tetrameric sodium-dianions, but the monomeric radical-anion. The reaction rates were proportional to the reciprocals of the molecular weights of the macromonomers.