Synthesis of well-defined dendritic hyperbranched polymers by iterative methodologies using living/controlled polymerizations
Synthesis of well-defined dendritic hyperbranched polymers by iterative methodologies using living/controlled polymerizations
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DOI：
10.1002/pi.2361
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发表时间：
2008-04
影响因子：
3.2
通讯作者：
A. Hirao;K. Sugiyama;A. Matsuo;Yuji Tsunoda;Takumi Watanabe
中科院分区：
文献类型：
--
作者：
A. Hirao;K. Sugiyama;A. Matsuo;Yuji Tsunoda;Takumi Watanabe
本文首先介绍了利用活性/可控聚合的基于生成的生长方法合成具有明确结构的各种枝状超支化聚合物。其次，介绍了用新的迭代方法合成树枝状超支化聚甲基丙烯酸甲酯（pmma）及其官能嵌段共聚物的方法。该方法涉及每个迭代过程中的两个反应顺序：(a) α-功能化的活阴离子PMMA与叔丁基二甲基硅氧基甲基苯基（SMP）基团与溴化苄（BnBr）链端功能化聚合物的连接反应；(b) SMP基团转化为BnBr功能的反应。这个反应顺序重复几次，以构建高代（最多第七代）枝状超支化聚合物。类似的支链嵌段共聚物也已经用相同的迭代方法用其他α-功能化的活阴离子聚合物合成。用x射线光电子能谱和接触角测量对PMMA和聚（2-（全氟丁基）甲基丙烯酸乙酯）段组成的枝状超支化嵌段共聚物的表面结构进行了表征。根据枝状超支化pmma的固有粘度、g′值和Rh值，讨论了枝状超支化pmma的溶解行为。版权所有©2007化工学会
This review presents firstly the synthesis of various dendritic hyperbranched polymers with well-defined structures by generation-based growth methodologies using living/controlled polymerization. Secondly, the synthesis of dendritic hyperbranched poly(methyl methacrylate)s (PMMAs) and their functionalized block copolymers using a novel iterative methodology is described. The methodology involves a two-reaction sequence in each iterative process: (a) a linking reaction of α-functionalized living anionic PMMA with tert-butyldimethylsilyloxymethylphenyl (SMP) groups with benzyl bromide (BnBr)-chain-end-functionalized polymer and (b) a transformation reaction of the SMP groups into BnBr functions. This reaction sequence is repeated several times to construct high-generation (maximum seventh generation) dendritic hyperbranched polymers. Similar branched architectural block copolymers have also been synthesized by the same iterative methodology using other α-functionalized living anionic polymers. Surface structures of the resulting dendritic hyperbranched block copolymers composed of PMMA and poly(2-(perfluorobutyl)ethyl methacrylate) segments have been characterized using X-ray photoelectron spectroscopy and contact angle measurements. Solution behaviors of dendritic hyperbranched PMMAs with different generations and branch densities are discussed based on their intrinsic viscosities, g′ values and Rh values. Copyright © 2007 Society of Chemical Industry