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

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• 作者：Kazuhiro Dohi ; Yoshikatsu Tsuchiya ; Kiyoshi Endo ; Asuka ; Masumoto ; Hideya Kawasaki ; Ryuichi Arakawa
• 刊名：Macromolecules
• 出版年：2011
• 出版时间：April 12, 2011
• 年：2011
• 卷：44
• 期：7
• 页码：1808-1813
• 全文大小：887K
• 年卷期：v.44,no.7(April 12, 2011)
• ISSN：1520-5835

文摘

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鈭扝 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路HCl) obtained by the thiol鈭抏ne reaction of the macromonomer with 2-(diethylamino)ethanethiol hydrochloride was conducted. The MALDI mass spectrum of PVC-DEA路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路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/BuLi = 10) was the most syndiotactic polymer (rr > 80%).