Insights and comparison of structure–bulk property relationships in low generation hydroxylated polyester dendrimer and hyperbranched polymer prepared from bis-MPA monomer
Insights and comparison of structure–bulk property relationships in low generation hydroxylated polyester dendrimer and hyperbranched polymer prepared from bis-MPA monomer
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DOI：
10.1016/j.polymer.2021.124097
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发表时间：
2021-08
期刊：
影响因子：
4.6
通讯作者：
Beibei Chen;M. Syed;Samantha P. Daymon;B. Olson;Oluwapelumi O. Kareem;Joseph A. Giesen;Gregory B. Fahs;R. R. Moore-R.;Scott M. Grayson;S. Nazarenko
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文献类型：
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作者：
Beibei Chen;M. Syed;Samantha P. Daymon;B. Olson;Oluwapelumi O. Kareem;Joseph A. Giesen;Gregory B. Fahs;R. R. Moore-R.;Scott M. Grayson;S. Nazarenko
在这项研究中，第二代，完全支化的树枝状大分子（D2）的合成使用迭代的方法通过酸酐偶联从双MPA单体和季戊四醇核心。这种树枝状聚合物在实验室中的多克规模生产使结构-本体性质关系的多方面研究成为可能，并随后与第二代化学相似但超支化的聚合物（HBP 2）进行比较，该聚合物通过快速一锅法合成从双MPA单体和乙氧基化季戊四醇核心产生。几个表征工具，如1H NMR，FTIR，DSC，WAXS，和高压衍射分析，阐明这两个重要的树枝状聚合物子类之间的根本差异和相似之处。具体而言，高压电测法允许调查的温度和压力对特定体积（PVT）的树枝状聚合物和它的HBP类似物的影响。拟合PVT数据的Simha-Somcynsky（S-S）状态方程（EOS）的熔融状态，使演示的电源，这个EOS，最初开发的线性聚合物，也充分描述了PVT表面的树枝状聚合物和HBP在这项研究中。从S-S模型生成的分子参数进行了比较与其他聚合物体系。最后，树枝状聚合物和HBP的自由体积分数，从PVT数据和S-S模型确定，在不同的温度和压力进行了比较。
In this study a second generation, perfectly branched dendrimer (D2) was synthesized using an iterative method via anhydride coupling from a bis-MPA monomer and a pentaerythritol core. The multigram scale production of this dendrimer in the lab enabled a multifaceted investigation of structure-bulk property relationships and a subsequent comparison with those of the second generation of a chemically similar but hyperbranched polymer (HBP2) produced via rapid one-pot synthesis from a bis-MPA monomer and an ethoxylated pentaerythritol core. Several characterization tools such as1H NMR, FTIR, DSC, WAXS, and high-pressure dilatometry were employed to explicate fundamental differences and similarities between these two important dendritic polymer subclasses. Specifically, high pressure dilatometry permitted an investigation of temperature and pressure effects on specific volume (PVT) of the dendrimer and its HBP analogue. Fitting PVT data to the Simha-Somcynsky (S–S) equation of state (EOS) for the melt state enabled demonstration the power of this EOS, originally developed for linear polymers, to also fully describe the PVT surfaces of the dendrimer and HBP in this study. Generated molecular parameters from the S–S model were compared with those for other polymeric systems. Finally, fractional free volume for the dendrimer and HBP, determined from the PVT data and the S–S model, at various temperatures and pressures was compared.