A Novel One-Pot Procedure for the Fast and Efficient Conversion of RAFT Polymers into Hydroxy-Functional Polymers
A Novel One-Pot Procedure for the Fast and Efficient Conversion of RAFT Polymers into Hydroxy-Functional Polymers
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DOI：
10.1071/ch09080
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发表时间：
2009-09
影响因子：
1.1
通讯作者：
Till Gruendling;Till Gruendling;Mathias Dietrich;Mathias Dietrich;C. Barner‐Kowollik
中科院分区：
文献类型：
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作者：
Till Gruendling;Till Gruendling;Mathias Dietrich;Mathias Dietrich;C. Barner‐Kowollik
我们报告的成功定量转化的甲基丙烯酸酯和丙烯酸酯型聚合物制备的可逆加成-断裂链转移（RAFT）聚合进行二硫酯端基羟基官能的聚合物。简单的反应程序包括在空气存在下在高温（T = 60°C）下搅拌二硫酯封端的聚合物和偶氮引发剂在四氢呋喃中的溶液。该反应定量地产生氢过氧化物官能团，其可以在一锅法中使用三苯基膦有效地还原为羟基。采用体积排阻色谱-电喷雾质谱法监测反应进程。新的主链连接的羟基基团提供了用于化学端基转化和与制备的RAFT聚合物的缀合反应的通用锚，这解决了二硫酯端基进行非自由基转化的能力相当有限的问题。
We report on the successful quantitative transformation of methacrylate and acrylate-type polymers prepared by reversible addition–fragmentation chain transfer (RAFT) polymerization carrying a dithioester-end-group into hydroxy-functional polymers. The simple reaction procedure involves stirring a solution of the dithioester-capped polymer and an azo-initiator in tetrahydrofuran at elevated temperatures (T = 60°C) in the presence of air. This reaction quantitatively yields hydroperoxide functionalities that can be efficiently reduced to hydroxy groups in a one-pot procedure using triphenylphosphine. Size exclusion chromatography–electrospray mass spectrometry was employed to monitor the progress of the reaction. The new backbone-linked hydroxy group provides a versatile anchor for chemical end-group conversions and conjugation reactions with prepared RAFT polymers, which alleviates problems with the rather limited ability of the dithioester-end-group to undergo non-radical transformations.