Thermal polymerizations of alkali 4-(2-bromoethyl)benzoates in bulk

✍ Scribed by Fumihiko Akutsu; Mari Inoki; Koichi Shinoda; Takashi Susukida; Yoshio Kasashima; Tadashi Shimura; Masaomi Tsuchiya

• Book ID: 101273540
• Publisher: John Wiley and Sons
• Year: 1999
• Tongue: English
• Weight: 114 KB
• Volume: 37
• Category: Article
• ISSN: 0887-624X
• DOI: 10.1002/(sici)1099-0518(19990701)37:13<2055::aid-pola19>3.0.co;2-y

✦ Synopsis

Thermal polymerizations of alkali 4-(2-bromoethyl)benzoates (2-BEBAs) were investigated. The polymerization of the lithium salt at 220°C for 2 h under reduced pressure in bulk, followed by esterification, produced poly(methyl 4-vinylbenzoate), having a number-average molecular weight (M n ) of 9500 in a 54% yield. Thus, elimination of hydrogen bromide to form a double bond occurred, followed by vinyl polymerization. In contrast, polymerization of the potassium salt at 200°C for 2 h afforded poly(oxycarbonyl-1,4-phenylene-ethylene) (polyester 1), having an inherent viscosity of 0.19 dL g Ϫ1 in a 95% yield: i.e., polycondensation proceeded to afford the polyester. Reaction of the sodium salt at 220°C for 2 h produced polyester 1 having M n of 4000 in a 28% yield as well as 4-vinylbenzoic acid in a 9% yield. In the reaction of the sodium salt, both polycondensation and double bond formation occurred. Thus, these polymerizations depended on the counter cations of 2-BEBAs.