Konkolewicz Dominik, Schröder Kristin, Buback Johannes, Bernhard Stefan, Matyjaszewski Krzysztof
Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, Pennsylvania 15213, United States.
ACS Macro Lett. 2012 Oct 16;1(10):1219-1223. doi: 10.1021/mz300457e. Epub 2012 Oct 4.
Photochemically induced ATRP was performed with visible light and sunlight in the presence of parts per million (ppm) copper catalysts. Illumination of the reaction mixture yielded polymerization in case of 392 and 450 nm light but not for 631 nm light. Sunlight was also a viable source for the photoinduced ATRP. Control experiments suggest photoreduction of the Cu complex (ligand to metal charge transfer in the excited state), yielding a Cu complex, and a bromine radical that can initiate polymerization. No photoactivation of Cu complex was detected. This implies that the mechanism of ATRP in the presence of light is a hybrid of ICAR and ARGET ATRP. The method was also used to synthesize block copolymers and polymerizations in water.
在百万分之几(ppm)的铜催化剂存在下,利用可见光和阳光进行光化学诱导的原子转移自由基聚合(ATRP)。照射反应混合物时,392和450nm的光可引发聚合反应,但631nm的光则不能。阳光也是光诱导ATRP的可行光源。对照实验表明,铜配合物发生了光还原(激发态下配体到金属的电荷转移),生成了一种铜配合物和一个可引发聚合反应的溴自由基。未检测到铜配合物的光活化现象。这意味着在光照条件下,ATRP的机理是引发剂连续再生催化剂原子转移自由基聚合(ICAR ATRP)和活化剂再生的电子转移生成催化剂原子转移自由基聚合(ARGET ATRP)的混合机理。该方法还用于合成嵌段共聚物以及在水中进行聚合反应。