Precise Synthesis of End-Functionalized Poly(vinyl chloride) with Butyllithium

Autor: Yoshikatsu Tsuchiya, Hideya Kawasaki, Kazuhiro Dohi, Kiyoshi Endo, Masumoto Asuka, Ryuichi Arakawa
Rok vydání: 2011
Předmět:
Zdroj: Macromolecules. 44:1808-1813
ISSN: 1520-5835
0024-9297
DOI: 10.1021/ma200042e
Popis: The polymerization of vinyl chloride (VC) with n- or tert-butyllithium (n- or tert-BuLi) in the presence of allyl bromide (ABr) was evaluated for synthesizing the vinyl-terminated poly(vinyl chloride) macromonomer (PVCM). The structure of the product was based on the 1H NMR and H−H COSY spectra. The functionality of the vinyl group was over 90%. To determine the detailed structure of PVCM, a MALDI-TOF-MS analysis of the PVCM derivative (PVC-DEA·HCl) obtained by the thiol−ene reaction of the macromonomer with 2-(diethylamino)ethanethiol hydrochloride was conducted. The MALDI mass spectrum of PVC-DEA·HCl in the absence of any ionizers exhibited only one series of ions repeating at an interval of 62 Da (which was the repeating VC unit), and the mass distribution agreed well with the calculated value of PVC-DEA·H+ without any defect structures. The syndiotactic rich PVC was found to be synthesized by the polymerization of VC with BuLi in the presence of ABr. Especially, the obtained PVCM using tert-BuLi (ABr/...
Databáze: OpenAIRE