Analysis of association constant for ground state dye-electron acceptor complex of photoinitiator systems and the association constant effect on the kinetics of visible-light-induced polymerizations.
Analysis of association constant for ground state dye-electron acceptor complex of photoinitiator systems and the association constant effect on the kinetics of visible-light-induced polymerizations.
复制标题
光引发剂体系基态染料-电子受体复合物的缔合常数分析以及缔合常数对可见光诱导聚合动力学的影响。
DOI：
10.1002/pola.23252
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发表时间：
2009-03-01
影响因子：
--
通讯作者：
Stansbury, Jeffrey W.
中科院分区：
文献类型：
--
作者：
Kim, Dongkwan;Scranton, Alec B.;Stansbury, Jeffrey W.
我们研究了氧杂蒽染料（玫瑰红（RB）和荧光素（FL））与溶于甲基丙烯酸羟乙酯（HEMA）单体的二苯基碘鎓盐（DPI）之间基态给体/受体复合物的形成。为了表征络合物的缔合常数，我们提出了一个新的分析模型的基础上的Benesi-Hildebrand模型。由于原始Benesi-Hildebrand模型的假设是吸收带仅归因于络合物的存在，并且自由组分的吸收可以忽略不计;该模型不能应用于我们的系统，这是基于染料的引发剂系统。对于每种染料，基态络合物的摩尔吸光系数作为波长的函数进行了评价，这种分析证实了修改后的贝内西-希尔德布兰德模型的有效性。此外，我们观察到RB/DPI光引发剂体系不能产生可察觉的聚合速率，但FL/DPI光引发剂体系提供非常高的聚合速率。基于这些配合物的缔合常数，我们得出结论，所观察到的动力学差异来自于基态染料受体配合物的不同缔合常数值，导致背电子转移反应。
We investigated the formation of ground state donor/acceptor complexes between xanthene dyes (rose Bengal (RB) and fluorescein (FL)) and a diphenyl iodonium salt (DPI) which is dissolved in 2-hydroxyethyl methacrylate (HEMA) monomer. To characterize the association constant of the complex, we have suggested a new analysis model based upon the Benesi-Hildebrand model. Because the assumption of the original Benesi-Hildebrand model is that the absorption bands are due only to the presence of the complex and that the absorption by the free component is negligible; the model cannot be applied to our systems, which is a dye-based initiator system. For each dye, the molar absorptivity of the ground state complex was evaluated as a function of wavelength and this analysis confirmed the validity of the modified Benesi-Hildebrand model. In addition, we observed the RB/DPI photoinitiator system failed to produce a perceptible polymerization rate but the FL/DPI photoinitiator system provided very high rates of polymerization. Based upon the association constant for these complexes, we concluded that the observed kinetic differences arise from the different association constant values of the ground state dye-acceptor complex, resulting in back electron transfer reaction.
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