Multifunctional Polymerization Kinetics and Network Structure Thereof

摘要- Peppas - 9311563 高交联聚合物作为信息存储系统、非球面透镜和光纤涂层材料具有潜在的用途。 制造这些材料的要求包括快速聚合速率、聚合时的低体积收缩、聚合物的高尺寸和热稳定性以及聚合物网络内的最小结构不均匀性。 聚二甲基丙烯酸酯目前用于许多应用中;通常由二甲基丙烯酸酯单体生产。 这些反应是缓慢的，它们可能需要30-40分钟才能达到liniting转化。 丙烯酸酯单体的反应速度快七到十倍，因此是更好的研究聚合体系。 本研究将探讨多官能聚合/交联反应的数学模型。 建立了预测聚合反应全过程引发剂效率的理论模型。 传播和终止速率常数的基本描述也将被开发。 这些表达式将被纳入到典型的启动-传播-终止机制和模型模拟将进行。 将进行动力学胶凝模拟，以确定在指定反应条件下的最终网络结构。 将通过暴露于UV光来研究聚乙二醇二丙烯酸酯网络的聚合/交联。 将测定聚合时的体积收缩率、溶胀特性、交联之间的分子量、所得网络的玻璃化转变温度和热稳定性，并用于分析交联结构。 通过改变两个C=C键之间的乙二醇单元的长度，将研究这些聚合反应的动力学变化。 转换时间的配置文件将获得在不同的光强度使用量热和光谱技术。 通过结构限制乙烯9 9 9 9 9 9 9 9摘要- Peppas - 9311563 高度交联的聚合物作为信息存储系统材料具有潜在的用途， L 不 ^ G O Z \ L ! ! D ! ! O L ( Times New Roman 符号Arial | V ^ L 不 ' ^ 6 G J " H A %F % / 玛丽亚·K布尔卡玛丽亚K。布尔卡

Abstract - Peppas - 9311563 Highly crosslinked polymers have potential uses as materials for information storage systems, aspherical lenses and optical fiber coatings. The requirements for the manufacture of these materials include a rapid polymerization rate, low volume shrinkage on polymerization, high dimensional and thermal stability of the polymer, and minimal structural inhomogeneities within the polymer network. Polydimethacrylates are currently used in many applications; often produced from dimethacrylate monomers. These reactions are slow, they may take 30-40 minutes to reach liniting conversions. Acrylate monomers react seven to ten times faster and are therefore better polymerization systems to study. The mathematical modeling of multifunctional polymerization/crosslinking reactions will be investigated in this research project. A theoretical model for the prediction of initiator efficiency thoughout the course of the polymerization will be developed. Fundamental descriptions for the propagation and termination rate constants will also be developed. These expressions will be incorporated into the typical initiation-propagation-termination mechanism and model simulations will be carried out. Kinetic gellation simulations will be carried out to determine the final network structure at the specified reaction conditions. Polymerization/crosslinking of polyethylene glycol diacrylate networks will be studied by exposure to UV light. Volume shrinkage on polymerization, swelling characteristics, molecular weight between crosslinks, glass transition temperature and thermal stability of the resulting networks will be determined and used to analyze the crosslinked struture. By varying the length of the etylene glycol unit between the two C=C bonds, changes in the kinetics of these polymerizations will be studied. The conversion-time profiles will be obtained at different light intensities using a calorimetric and a spectroscopic technique. limitingthroughoutstructureethylene9 9 9 9 9 9 9 9 9Abstract - Peppas - 9311563 Highly crosslinked polymers have potential uses as materials for information storage systems, asp L T ^ g o Z \ L ! ! D ! ! o L ( Times New Roman Symbol & Arial | V ^ L T ' ^ 6 g J " h A %F % / Maria K. Burka Maria K. Burka