Gradient polymer elution chromatographic analysis of α,ω-dihydroxypolystyrene synthesized via ATRP and click chemistry
Gradient polymer elution chromatographic analysis of α,ω-dihydroxypolystyrene synthesized via ATRP and click chemistry
复制标题
DOI：
10.1021/ma051566g
复制
发表时间：
2005-11-01
期刊：
影响因子：
5.5
通讯作者：
Matyjaszewski, K
中科院分区：
文献类型：
--
作者：
Gao, HF;Louche, G;Matyjaszewski, K
导言。在过去的十年里，可控/活性自由基聚合(CRP)的发展使得合成(Co)聚合物不仅具有预定的聚合度和窄的分子量分布(低多分散性，MW/Mn)，而且还具有高官能度和所需的微观结构。最有效的CRP方法之一是原子转移自由基聚合(ATRP)。2-4ATRP产生的聚合物保留了末端的卤素原子(S)，并可以通过适当的转化，特别是亲核取代，成功地转化为各种端基。例如，用叠氮阴离子取代聚合物链末端的卤素原子是非常有效的。6所得到的有机叠氮基可以用于各种化学转化，以产生多种类型的末端官能团，例如氨基、羟基或羧基。有机叠氮化合物的一个特殊反应是叠氮化物和末端炔的1，3-偶极环加成反应。11两个小组最近报道，在铜(I)催化剂的作用下，这种偶联反应在温和的反应条件下得到了高特异性和高效率的1，4-二取代1，2，3-三氮唑产物。这些反应可以在水或有机介质中进行，几乎没有观察到副反应。由于铜(I)催化的偶联反应的实用性和多功能性，使其被归类为有效和特定的有机反应，通常被称为“点击反应”，如夏普莱斯等人所创造的那样。14点击反应已成为修饰链端和/或链侧基团的有效方法，用于各种(共)聚合物的官能化。15-17由于ATRP在制备功能遥爪聚合物方面的应用，结合点击化学的效率，是合成各种末端官能化聚合物的一种有趣和有前途的策略。18最近，几个基团报道了通过ATRP和随后的点击反应合成功能性(Co)聚合物。19-21，46值得注意的是，Lutz等人。介绍了ATRP法合成的叠氮化聚合物与不同种类的炔烃反应制备单功能聚合物的方法。20开发和优化合成明确定义的功能聚合物的程序是
Introduction. In the past decade, the development of controlled/living radical polymerizations (CRP) 1 allows the synthesis of (co) polymers not only with a predetermined degree of polymerization and narrow molecular weight distribution (low polydispersity, Mw/Mn) but also with high functionality and desired microstructure. One of the most efficient CRP methods is atom transfer radical polymerization (ATRP). 2-4 The polymers produced by ATRP preserve the terminal halogen atom (s) and can be successfully converted into various end groups through appropriate transformation, especially nucleophilic substitutions. 5 For instance, the substitution of a halogen atom from a polymer chain end by an azide anion is very efficient. 6 The obtained organic azido group can be used for a variety of chemical transformations to produce numerous types of end functional moieties, 5, 7-10 such as amino, hydroxy, or carboxy groups.One particular reaction of organic azides that has garnered increased attention is the 1, 3-dipolar cycloaddition of azides and terminal alkynes. 11 Two groups recently reported that with the use of a Cu (I) catalyst this coupling reaction results in the highly specific and efficient preparation of 1, 4-disubstituted 1, 2, 3-triazole products under moderate reaction conditions. 12, 13 These reactions can be conducted in aqueous or organic media, and little or no side reactions are observed. The practicality and versatility of the Cu (I)-catalyzed coupling reaction led to its inclusion in the class of efficient and specific organic reactions, commonly termed “click reactions”, as coined by Sharpless et al. 14 Click reactions have emerged as a powerful method to modify chainend and/or chain-side groups for functionalization of various (co) polymers. 15-17 Because of its utility for the preparation of functional telechelic polymers, ATRP, combined with the efficiency of click chemistry, is an interesting and promising strategy to synthesize various end-functionalized polymers. 18 Recently, several groups have reported the synthesis of functional (co) polymers via ATRP and subsequent click reactions. 19-21, 46 Notably, Lutz et al. described the preparation of monofunctional polymers by reacting various alkynes with azide-derivatized polymers prepared by ATRP. 20 The development and optimization of procedures for the synthesis of well-defined functional polymers is