Cyclic polymers based on UV-induced strain promoted azide–alkyne cycloaddition reaction
Cyclic polymers based on UV-induced strain promoted azide–alkyne cycloaddition reaction
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DOI：
10.1039/c5py00416k
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发表时间：
2015-05
影响因子：
4.6
通讯作者：
Peng Sun;Qingquan Tang;Zhenpeng Wang;Yuming Zhao;Ke Zhang
中科院分区：
文献类型：
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作者：
Peng Sun;Qingquan Tang;Zhenpeng Wang;Yuming Zhao;Ke Zhang
将原子转移自由基聚合（ATRP）与紫外光诱导的应变促进叠氮-炔环加成（SPAAC）反应相结合，发展了一种制备环状聚合物的独特方法。借助于环丙烯酮掩蔽的二苯并环辛炔官能化ATRP引发剂（I-1），合成了在一个聚合物链端具有环丙烯酮掩蔽的二苯并环辛炔并且在另一个聚合物链端具有溴基团的定义明确的遥爪聚苯乙烯（PS）。然后利用单电子转移-氮氧自由基偶联反应将溴端基改性为叠氮化物，得到相应的线性PS前体。在紫外光照射下，二苯并环辛炔的端基从环丙烯酮掩蔽的二苯并环辛炔中定量释放出来，与叠氮端基原位发生分子内反应，使线型PS前体闭环，并基于SPAAC点击反应生成相应的环状PS。
A unique method was developed for the preparation of cyclic polymers based on the combination of atom transfer radical polymerization (ATRP) and UV-induced strain promoted azide–alkyne cycloaddition (SPAAC) reaction. By virtue of a cyclopropenone-masked dibenzocyclooctyne functionalized ATRP initiator (I-1), well-defined telechelic polystyrene (PS) was synthesized to have a cyclopropenone-masked dibenzocyclooctyne at one polymer chain end and a bromo group at the other. The single electron transfer-nitroxide radical coupling reaction was then used to modify the bromo end group to azide, resulting in the corresponding linear PS precursor. Under UV irradiation on its highly diluted solution, the dibenzocyclooctyne end group was quantitatively released from cyclopropenone-masked dibenzocyclooctyne, which intramolecularly reacted with the azide end group in situ to ring-close the linear PS precursor and produce the corresponding cyclic PS based on the SPAAC click reaction.