This manuscript describes a synthetic strategy and structure–property investigation of unprecedented phosphonium-based zwitterionic homopolymers (polyzwitterions) and random copolymers (zwitterionomers). Free radical polymerization of 4-(diphenylphosphino)styrene (DPPS) provided neutral polymers containing reactive triarylphosphines. Quantitative postpolymerization alkylation of these pendant functionalities generated a library of polymers containing various concentrations of neutral phosphines, phosphonium ions, and phosphonium sulfobetaine zwitterions. The zwitterionic homo- and copolymers exhibited significantly higher glass transition temperatures (T_g) and enhanced mechanical reinforcement in comparison to neutral and phosphonium analogues. These changes in T_g and mechanical properties were attributed to nanoscale morphological domains, which formed due to electrostatic interactions between zwitterionic groups, as revealed by X-ray scattering and broadband dielectric spectroscopy (BDS). BDS revealed increased static dielectric constants (>25) for the phosphonium zwitterionomers compared to ionomeric or neutral analogues. These high static dielectric constants for the solvent-free polyzwitterions supported their stronger polarization response in comparison with polymers containing neutral phosphines and phosphonium ions, and these interactions accounted for morphological differences and enhanced mechanical behavior. This work describes a versatile strategy for modulating electrostatic interactions with tunable mechanical properties for an unprecedented family of zwitterionic polymers.

中文翻译：

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磷基两性离子：离子结构和缔合对机械性能的影响

该手稿描述了前所未有的phospho基两性离子均聚物（多性两性离子）和无规共聚物（两性离子聚合物）的合成策略和结构性质研究。4-（二苯基膦基）苯乙烯（DPPS）的自由基聚合提供了含有反应性三芳基膦的中性聚合物。这些侧基官能团的定量后聚合烷基化生成了一个包含各种浓度的中性膦，phospho离子和phospho磺基甜菜碱两性离子的聚合物库。与中性和phospho类似物相比，两性离子均聚物和共聚物表现出明显更高的玻璃化转变温度（T _g）和增强的机械增强作用。T _g的这些变化X射线散射和宽带介电谱（BDS）揭示，由于两性离子基团之间的静电相互作用而形成的纳米级形貌结构域和力学性能。与离聚物或中性类似物相比，BDS显示出z两性离子聚合物的静态介电常数（> 25）增加。与包含中性膦和phospho离子的聚合物相比，这些无溶剂多两性离子的高静态介电常数支持了其更强的极化响应，并且这些相互作用导致了形态差异和增强的机械性能。这项工作描述了一种用于调节静电相互作用且具有可调节机械特性的通用策略，该策略可用于前所未有的两性离子聚合物系列。