Syndiotactic Polyallyltrimethylsilane-Based Stereoregular Diblock Copolymers: Syntheses and Self-Assembled Nanostructures

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• 作者：Jing-Yu Lee ; Min-Ching Shiao ; Fu-Yuan Tzeng ; Chin-Hung Chang ; Chih-Kuang Tsai ; Jing-Cherng Tsai ; Kuan-Hsin Lo ; Shih-Chieh Lin ; Rong-Ming Ho
• 刊名：Macromolecules
• 出版年：2012
• 出版时间：March 27, 2012
• 年：2012
• 卷：45
• 期：6
• 页码：2720-2730
• 全文大小：462K
• 年卷期：v.45,no.6(March 27, 2012)
• ISSN：1520-5835

文摘

Structurally well-defined stereoregular diblock copolymers composed of syndiotactic polyallyltrimethylsilane (sPATMS) and poly(methyl methacrylate) (PMMA) were prepared by using an 伪-bromoester-terminated sPATMS macroinitiator, which was chain extended by MMA using a cuprous halide-based atom transfer radical polymerization (ATRP) system. The 伪-bromoester-terminated sPATMS macroinitiator was prepared via the esterfication of hydroxyl-capped sPATMS with 伪-bromoisobutyryl bromide. The hydroxyl-capped sPATMS was generated via a selective chain transfer reaction to triethylaluminum (TEA) during the syndiospecific polymerization of allyltrimethylsilane (ATMS) conducted in the presence of syndiospecific ansa-metallocene catalysts. The proposed synthetic route not only offers the high-yield production of stereoregular sPATMS-b-PMMA but also provides the linking of the stereoregular block (sPATMS) with PMMA through a controlled/living radical polymerization process. Moreover, the proposed method offers effective control over the block chain length, the molecular weight distribution (M_w/M_n) and the stereoregularity of sPATMS block. Thus, the self-assembly of the resultant diblock copolymers produces well-ordered nanostructures from microphase separation, as evidenced by transmission electron microscopy and small-angle X-ray scattering results.