Multifunctional Polymerization Kinetics and Network Structure Thereof

多功能聚合动力学及其网络结构

• 批准号: 9311563
• 负责人: Nicholas Peppas
• 金额: $ 19.74万
• 依托单位: Purdue Research Foundation
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1993
• 资助国家: 美国
• 起止时间: 1993-08-15 至 1997-01-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9311563&HistoricalAwards=false
• 关键词: Multifunctional; Polymerization; Kinetics; Network; Structure

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

PEPAS-9311563高交联度聚合物在信息存储系统、非球面透镜和光纤涂层等方面具有潜在的应用前景。制造这些材料的要求包括聚合速度快，聚合时体积收缩小，聚合物的尺寸和热稳定性高，以及聚合物网络中的结构不均匀最小。聚二甲基丙烯酸酯目前用于许多应用；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分钟才能达到林肯转化。丙烯酸酯单体的反应速度快七到十倍，因此是更好的聚合体系来研究。本研究项目将对多官能团聚合/交联反应的数学模型进行研究。建立了考虑聚合过程的引发剂效率预测的理论模型。还将开发传播速率常数和终止速率常数的基本描述。将这些表达式结合到典型的起爆-传播-终止机制中，并进行模型模拟。在指定的反应条件下，将进行动力学模拟以确定最终的网络结构。聚乙二醇二丙烯酸酯网络的聚合/交联将在紫外光照射下进行研究。将测定聚合时的体积收缩、溶胀特性、交联物之间的相对分子质量、玻璃化转变温度和所得网络的热稳定性，并用于分析交联物的结构。通过改变乙二醇单元在两个C=C键之间的长度，将研究这些聚合反应动力学的变化。在不同的光强度下，将使用量热法和光谱技术获得转换时间分布。限制结构乙烯9 9 9抽象-PEPAS-9311563高度交联型聚合物具有作为信息存储系统材料的潜在用途，ASP L T^GoZ\L！！D！！O L(泰晤士报新罗马符号&AMP；宋体|V^L T‘^6 g J“h A%F%/玛丽亚·K·布卡玛丽亚·K·布尔卡