Synthesis of photocleavable linear macromonomers by ATRP and star macromonomers by a tandem ATRP-click reaction: Precursors to photodegradable model networks
Synthesis of photocleavable linear macromonomers by ATRP and star macromonomers by a tandem ATRP-click reaction: Precursors to photodegradable model networks
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DOI：
10.1021/ma062862b
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发表时间：
2007-05-15
期刊：
影响因子：
5.5
通讯作者：
Turro, Nicholas J.
中科院分区：
文献类型：
--
作者：
Johnson, Jeremiah A.;Finn, M. G.;Turro, Nicholas J.
采用原子转移自由基聚合（ATRP）和铜催化叠氮-炔环加成反应（CuAAC）两种互补的方法合成了光降解高分子材料。通过原子转移自由基聚合和末端基团修饰，合成了中心具有可光裂解官能团的线性叠氮遥爪大分子单体。这些大分子单体通过CuAAC与四官能炔交联以形成不溶性材料，所述不溶性材料在暴露于350 nm的UV光时降解以产生限定分子量的可溶性星星聚合物产物。作为对该方法的补充，通过一种新型的一锅法CuAAC/ATRP反应，然后进行端基修饰，制备了具有光可裂解臂和末端叠氮化物的四臂星星聚合物。将这些星星聚合物与线性双官能炔交联以产生不溶性材料，所述不溶性材料在暴露于UV光时降解以产生限定分子量的线性聚合物。
Atom transfer radical polymerization (ATRP) and the copper-catalyzed azide - alkyne cycloaddition (CuAAC) were utilized for the synthesis of photodegradable polymeric materials by two complementary schemes. Linear azido-telechelic macromonomers possessing a photocleavable functionality at the center were synthesized by ATRP and subsequent end-group modification. These macromonomers were cross-linked with a tetrafunctional alkyne by CuAAC to form insoluble materials which degraded upon exposure to UV light of 350 nm to yield soluble star polymer products of defined molecular weight. Complementary to this approach, four-armed star polymers possessing photocleavable arms and terminal azides were prepared by a novel one-pot CuAAC/ATRP reaction followed by end-group modification. These star polymers were cross-linked with a linear, bifunctional alkyne to yield insoluble materials which, upon exposure to UV light, degraded to yield linear polymers of defined molecular weight.