Quantitative structure–reactivity modeling of copper-catalyzed atom transfer radical polymerization
Quantitative structure–reactivity modeling of copper-catalyzed atom transfer radical polymerization
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DOI：
10.1039/c0py00058b
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发表时间：
2010-07
影响因子：
4.6
通讯作者：
F. Lena;C. Chai
中科院分区：
文献类型：
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作者：
F. Lena;C. Chai
在这项工作中，我们提出了第一个成功的应用，在计算机建模的建设之间的定量和预测关系的一组常数KACT，KDEACT和KATRP和各种ATRP催化剂和引发剂的结构和性能。结果是一致的，不仅与普遍接受的ATRP机理图片，但也提供了宝贵的见解，这一复杂的聚合反应。该模型，建立使用遗传函数近似算法，突出和量化的关键作用，在ATRP过程中发挥的催化剂和引发剂的能量和空间因素，以及由反应介质。此外，该模型表明存在的长程相互作用，在催化剂引发剂的识别和随后的结合。我们相信，该方法将被证明是一个强大的工具，发现改进的催化剂ATRP。
In this work, we present the first successful application of in silico modeling to the construction of quantitative and predictive relationships between the set of constants kact, kdeact and KATRP and the structures and properties of various ATRP catalysts and initiators. The results are consistent not only with the generally accepted ATRP mechanistic picture but also provide valuable insights into this complex polymerization reaction. The models, built using the genetic function approximation algorithm, highlight and quantify the pivotal roles played in the ATRP process by energetic and steric factors of both catalysts and initiators as well as by the reaction medium. Moreover, the models suggest the existence of long-range interactions in catalyst–initiator recognition and subsequent binding. We believe that the approach will prove to be a powerful tool for the discovery of improved catalysts for ATRP.