Nitroxide-Mediated Controlled Free Radical Polymerization of the Chelate Monomer 4-Styryl-tris(2-pyridyl)borate (StTpyb) and Supramolecular Assembly via Metal Complexation

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• 作者：Patrick O. Shipman ; Chengzhong Cui ; Patrycja Lupinska ; Roger A. Lalancette ; John B. Sheridan ; Frieder J盲kle
• 刊名：ACS Macro Letters
• 出版年：2013
• 出版时间：December 17, 2013
• 年：2013
• 卷：2
• 期：12
• 页码：1056-1060
• 全文大小：332K
• 年卷期：v.2,no.12(December 17, 2013)
• ISSN：2161-1653

文摘

The reaction of 4-(dibromoboryl)styrene with 2-pyridylmagnesium chloride resulted in the formation of 4-styryl-tris(2-pyridyl)borate free acid (StTypb), a new polymerizable nonpyrazolyl 鈥渟corpionate鈥?ligand. StTypb did not undergo self-initiated polymerization under ambient conditions and proved to slowly polymerize through standard radical polymerization at 90 掳C. Nitroxide-mediated polymerization (NMP) of StTypb at 135 掳C proceeded with good control, resulting in a polymer of M_n = 27400 and PDI = 1.21. The TEMPO-terminated homopolymer successfully initiated the polymerization of styrene, generating an amphiphilic block copolymer with DP_n of 1200 and 78 for the PS and the StTypb block, respectively. A similar block copolymer with DP_n of 29 and 20 for the PS and the StTypb block respectively was obtained in a reverse polymerization procedure from a PS macroinitiator. The self-assembly of these block copolymers was examined in selective solvents and preliminary metal complexation studies were performed.