Synthesis of Poly(methacrylic acid) Brushes via Surface-Initiated Atom Transfer Radical Polymerization of Sodium Methacrylate and Their Use as Substrates for the Mineralization of Calcium Carbonate

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• 作者：Stefano Tugulu ; Raphaë ; l Barbey ; Marc Harms ; Marc Fricke ; Dirk Volkmer ; Antonella Rossi ; Harm-Anton Klok
• 刊名：Macromolecules
• 出版年：2007
• 出版时间：January 23, 2007
• 年：2007
• 卷：40
• 期：2
• 页码：168 - 177
• 全文大小：1117K
• 年卷期：v.40,no.2(January 23, 2007)
• ISSN：1520-5835

文摘

This manuscript describes the synthesis of poly(methacrylic acid) (PMAA) brushes via surface-initiated atom transfer radical polymerization (SI-ATRP) of sodium methacrylate (NaMA) and their use as substratesfor the mineralization of calcium carbonate. A CuBr/CuBr₂/bipyridine catalyst system in aqueous solution atroom temperature allowed the synthesis of brushes with thicknesses of up to 300 nm. Using substrates modifiedwith mixtures of an ATRP-initiator modified trimethoxysilane and an "inert" pivaloyl-modified trimethoxysilaneto initiate the ATRP of NaMA, a series of brushes with varying chain density could be prepared. Subsequentmineralization experiments revealed that, while low-density brushes promoted the formation of calcite crystals,high-density brushes were covered with a thin layer of amorphous CaCO₃ (ACC). This is of interest becauseACC can serve as a metastable precursor for different crystalline CaCO₃ polymorphs and offers attractiveperspectives for the bottom-up fabrication of well-defined CaCO₃ crystal architectures.