Anionic synthesis of ω-dimethylamino-functionalized polymers by functionalization of polymeric organolithiums with 3-dimethylaminopropyl chloride

✍ Scribed by Quirk, Roderic P.; Han, Kwansoo; Lee, Youngjoon

• Publisher: John Wiley and Sons
• Year: 1999
• Tongue: English
• Weight: 310 KB
• Volume: 48
• Category: Article
• ISSN: 0959-8103
• DOI: 10.1002/(sici)1097-0126(199902)48:2<99::aid-pi101>3.0.co;2-u

✦ Synopsis

The functionalization reactions of polystyryllithium, polyisoprenyllithium and polybutadienyllithium in benzene with 3-dimethylaminopropyl chloride have been investigated in detail. The eþ ects of addition mode (normal and inverse addition), added Lewis bases (THF and TMEDA), temperature and concentration have been investigated. The polymer products were analysed by SEC, 1H and 13C NMR spectroscopy and end-group titration. The pure x-dimethylamino-functionalized polymers were quantitatively isolated by silica gel column chromatography. The functionalizations of polystyryllithium, polyisoprenyllithium and polybutadienyllithium by normal addition in benzene produce the corresponding x-dimethylamino-functionalized polymers in isolated yields of 67% , 85% and 90% , respectively. Functionalization efficiencies were improved by using the inverse addition procedure and by post-polymerization addition of Lewis bases before functionalization.