Photoinitiated Polymerization in Supercritical Fluids

超临界流体作为一种新型的流体， 处理流体，但几乎没有注意到作为介质， 进行化学转化。 的潜在优势 使用超临界流体反应作为介质的优点在于， 可以增加反应的选择性， 保持高转化率，溶解反应物和催化剂 在单一的流体相中， 均匀，并改善或大大促进 从反应物、催化剂和不需要的产物中分离产物 副产物，通过利用所表现出的相行为， 混合物在其临界区域。 这项研究的目的是 确定超临界流体中的变量如何影响 光引发聚合产物及动力学参数 流程. 系统研究确定链式反应 参数，如引发剂笼效应，低聚物/聚合物 分散性，齐聚物/聚合物立体化学，抑制率 常数和引发剂能量转移猝灭参数 将在二氧化碳中进行， 温度和压力。

Supercritical fluids have received widespread attention as processing fluids, but virtually no attention as media in which to carry out chemical transformations. The potential advantages of using a supercritical fluid reaction as a medium are that it may be possible to increase the selectivity of a reaction while maintaining high conversions, to dissolve reactants and catalyst in a single fluid phase so that the reaction occurs homogeneously, and to improve or greatly facilitate the separation of products from reactants, catalyst, and unwanted byproducts by utilizing the phase behavior exhibited by the mixture in its critical region. The goal of this research is to determine how the variables in supercritical fluids affect the products and kinetic parameters of photoinitiated polymerization processes. Systematic studies to determine chain-reaction parameters, such as initiator cage effects, oligomer/polymer dispersivity, oligomer/polymer stereochemistry, inhibition rate constants, and initiator energy-transfer quenching parameters will be carried out in carbon dioxide as a function of temperature and pressure.