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首页> 外文期刊>Journal of Applied Polymer Science >Reactivity Ratios and Copolymer Composition Evolution During Styrene/Dimethacrylate Free-Radical Crosslinking Copolymerization
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Reactivity Ratios and Copolymer Composition Evolution During Styrene/Dimethacrylate Free-Radical Crosslinking Copolymerization

机译：苯乙烯/二甲基丙烯酸酯自由基交联共聚过程中的反应率和共聚物组成演变

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摘要

In this article, experimental and simulated results are presented for the evolution of the copolymer composition as unsaturations are consumed in the free-radical cross-linking copolymerization of Styrene(St) and BisphenolA glycerolate dimethacrylate (BDMA). Real time FTIR measurements were performed to monitor the depletion of each comonomer double bond during the isothermal curing reaction at 80 degrees C. From the experimental data corresponding to different feed compositions, the initial reactivity ratios and their evolution with conversion were determined via a nonlinear least squares optimization of the integrated form of the copolymerization equation. The reactivity ratio of St increases continuously and exponentially with the overall reaction conversion, while that of BDMA decreases linearly. A modified terminal copolymerization model including the dependence of the reactivity ratios with the overall conversion was proposed. The application of this model provides a consistent fitting for the conversion of each comonomer during all reaction stages, even at high conversion values where large diffusion and topological restrictions for chain movements are present. Simulations show that the concentration of styrene units added to the copolymer increases with the overall reaction conversion, while that for the BDMA double bonds diminishes. Structures rich in homopolymerized styrene are predicted at later stages of the reaction.
机译：在本文中，由于苯乙烯（St）和双酚A甘油酸酯二甲基丙烯酸酯（BDMA）的自由基交联共聚反应中不饱和度的消耗，给出了共聚物组成演变的实验和模拟结果。进行实时FTIR测量以监测80°C等温固化反应过程中每个共聚单体双键的消耗情况。根据对应于不同进料组成的实验数据，通过非线性最小二乘法确定初始反应性比及其随转化的演变聚合方程积分形式的平方优化。随着整个反应转化率的增加，St的反应率呈连续和指数增长，而BDMA的反应率呈线性下降。提出了一种改进的末端共聚模型，该模型包括反应率与总转化率的关系。该模型的应用为所有共聚单体在所有反应阶段的转化提供了一致的拟合，即使在存在较大扩散和链运动拓扑限制的高转化率条件下也是如此。模拟表明，添加到共聚物中的苯乙烯单元的浓度随总反应转化率而增加，而对于BDMA双键的浓度则降低。预计在反应的后续阶段富含均聚苯乙烯的结构。

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