Molecular Simulations of Thermoset Polymers Implementing Theoretical Kinetics with Top-Down Coarse-Grained Models,Macromolecules

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Molecular Simulations of Thermoset Polymers Implementing Theoretical Kinetics with Top-Down Coarse-Grained Models
Macromolecules ( IF 5.1 ) Pub Date : 2020-03-25 , DOI: 10.1021/acs.macromol.9b02255
Amulya K. Pervaje ₁ , Joseph C. Tilly ₁ , Andrew T. Detwiler ₂ , Richard J. Spontak _{1,

3} , Saad A. Khan ₁ , Erik E. Santiso ₁

Affiliation

Thermoset polymers are examples of chemically cured, network-forming materials whose bulk properties depend sensitively on formulation chemistry and reaction conditions. In this work, we employ molecular dynamics simulations to model polyester-based urethane thermosets that are specifically targeted for coating applications. Parameterizing force field interactions with a statistical associating fluid theory (SAFT)-γ Mie approach in conjunction with corresponding state correlations [Mejía, A.; Ind. Eng. Chem. Res. 2014, 53, 4131−4141; Müller, E. A.; Langmuir 2017, 33, 11518–11529] permits the facile development of effective models for our thermosetting system. We have devised a theoretical model to fit experimental kinetic data and implement a crosslinking algorithm that replicates the theoretical kinetics. Our molecular simulations capture the cure kinetics regarding the reactions of the isocyanate group with the primary and secondary hydroxyl termini. Analysis of molecular-level connections that arise during crosslinking affords new information about network structure development. Predicted glass transition temperatures and thermomechanical properties agree well with experimental data.

中文翻译：

自上而下的粗粒模型实现理论动力学的热固性聚合物的分子模拟

热固性聚合物是化学固化的网络形成材料的示例，其本体性质敏感地取决于配方化学和反应条件。在这项工作中，我们采用分子动力学模拟来建模专门针对涂料应用的聚酯基聚氨酯热固性塑料。使用统计缔合流体理论（SAFT）-γMie方法结合相应的状态相关参数化力场相互作用[Mejía，A。; 工业工程师化学 Res。 2014，53，4131-4141;EAMüller; 朗缪尔 2017年，33，11518-11529]允许的有效模式轻便开发，为热固性系统。我们设计了一个理论模型来拟合实验动力学数据，并实现了一种可复制理论动力学的交联算法。我们的分子模拟记录了异氰酸酯基团与伯羟基和仲羟基末端反应的动力学。对交联过程中出现的分子级连接的分析提供了有关网络结构发展的新信息。预测的玻璃化转变温度和热机械性能与实验数据吻合良好。

更新日期：2020-04-24

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