Synthesis of cyclic polyelectrolyte via direct copper(I)-catalyzed click cyclization
Synthesis of cyclic polyelectrolyte via direct copper(I)-catalyzed click cyclization
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直接铜(I)催化点击环化合成环状聚电解质
DOI：
10.1002/pola.25869
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发表时间：
2012-03
期刊：
影响因子：
--
通讯作者：
Zhang, Guangzhao
中科院分区：
文献类型：
--
作者：
Chen, Fenggui;Liu, Guangming;Zhang, Guangzhao
聚电解质由于其在各个领域的应用前景而受到广泛关注。1由于环状结构的性质通常由其构象决定，2与直链结构相比，环状结构具有一些独特的性质。3然而，由于环戊二烯基聚合物的合成具有挑战性，对这类特殊聚合物的实验研究很少报道。4由于静电排斥作用会阻碍直链顺式顺5另一方面，尽管人们在环状聚合物的合成方面进行了大量的尝试，6-9新合成方法的设计和开发仍然是这一领域的重要课题。8目前，具有两个互补反应性端基的线性前体在稀溶液中的闭环反应已被广泛用于合成环状聚合物。9-13有机叠氮和炔的Huisgen 1，3-偶极环加成反应由于这两个基团之间的高反应性和对副反应的低敏感性而被证明在线性聚合物的环化中是有效的。11，14，15线性前体通常通过原子转移自由基聚合（ATRP）制备，因为末端Br基团可以以合理的产率容易地转化为叠氮化物。16-18含炔基的引发剂通常用四甲基硅烷（TMS）或三异丙基硅烷（TIPS）保护，以便消除随后聚合中的副反应，特别是在环状聚（丙烯酸叔丁酯）（PtBA）的合成中。通常使用四丁基氟化铵（TBAF）除去18、19 TMS或TIPS用于下一次点击环化。然而，叠氮基团在脱保护过程中通常从聚合物链的末端脱离，这将阻止下一次点击环化。
INTRODUCTION Polyelectrolyte has received extensive attention due to its promising applications in various fields. 1 As the properties of polyelectrolyte are generally determined by its conformation, 2 cyclic polyelectrolyte is expected to exhibit some unique properties in comparison with the linear one. 3 However, due to the challenge in synthesis of cyclic polyelectrolyte, the experimental studies on such special polymer are rarely reported. 4 A feasible method to synthesize cyclic polyelectrolyte should be based on the ionization of its neutral precursor as the electrostatic repulsion would prevent the direct cyclization of the linear polyelectrolyte chain. 5On the other hand, although a number of attempts have been devoted to the synthesis of cyclic polymer, 6–9 design and development of new synthetic methods are still the important subjects in this area. 8 Currently, the ring-closure reaction of linear precursor with two complementary reactive terminal groups in dilute solution has been extensively used to synthesize cyclic polymer. 9–13 Huisgen 1, 3-dipolar cycloaddition reaction of organic azide and alkyne proves to be efficient in the cyclization of linear polymer due to the high reactivity between such two groups and the low susceptibility to side reactions. 11, 14, 15 The linear precursor is usually prepared by atom transfer radical polymerization (ATRP), because the terminal Br group can be readily converted into azide with a reasonable yield. 16–18 The alkynylcontaining initiator is generally protected with tetramethylsilane (TMS) or triisopropylsilane (TIPS) so that the side reactions in the following polymerization are eliminated, especially in the synthesis of cyclic poly (tert-butyl acrylate)(PtBA). 18, 19 TMS or TIPS is usually removed using tetrabutylammonium fluoride (TBAF) for the next click cyclization. However, the azide groups are often detached from the ends of polymer chains in the deprotection process, which would prevent the next click cyclization.
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影响因子：
2
作者：
Cuevas, Felix;Oliva, Ana I.;Pericas, Miquel A.
通讯作者：
Pericas, Miquel A.
DOI：
10.1002/(sici)1099-0518(19990701)37:13
发表时间：
1999-07
期刊：
Journal of Polymer Science Part A
影响因子：
--
作者：
Mingqing Chen;T. Serizawa;A. Kishida;M. Akashi
通讯作者：
Mingqing Chen;T. Serizawa;A. Kishida;M. Akashi
DOI：
10.1002/1099-0518(200012)38:1
发表时间：
2000-01-01
影响因子：
--
作者：
Fraser, CL;Smith, AP
通讯作者：
Smith, AP
影响因子：
4.6
作者：
Gang‐Yin Shi;C. Pan
通讯作者：
Gang‐Yin Shi;C. Pan
影响因子：
5.5
作者：
Yongquan Dong;Yin-yin Tong;Botao Dong;F. Du;Zi‐Chen Li
通讯作者：
Yongquan Dong;Yin-yin Tong;Botao Dong;F. Du;Zi‐Chen Li