Selective Oxidation of Polysulfide Latexes to Produce Polysulfoxide and Polysulfone in a Waterborne Environment.
Selective Oxidation of Polysulfide Latexes to Produce Polysulfoxide and Polysulfone in a Waterborne Environment.
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DOI：
10.1021/acs.macromol.1c00382
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发表时间：
2021-04-27
期刊：
影响因子：
5.5
通讯作者：
Thérien-Aubin H
中科院分区：
文献类型：
--
作者：
Infante Teixeira L;Landfester K;Thérien-Aubin H
主链上含有高氧化态硫中心的聚合物，如聚亚硫醚和聚砜，具有良好的热机械稳定性和化学稳定性。为了避免它们具有挑战性的直接合成，已经开发了基于母体多硫化物氧化的方法，但受到不受控制的反应的困扰，导致聚亚硫醚和聚砜的混合物不明确，或者由于聚合物的过氧化导致聚砜的聚合度降低。我们开发了一种替代方法，在水性胶体乳液中使用不同的氧化剂来控制最终材料中硫的氧化状态，从而生产出定义良好的聚亚硫醚和聚砜。水性聚硫醚乳液的直接氧化避免了使用挥发性有机溶剂，并允许控制硫原子的氧化态。用叔丁基氢过氧化氢氧化母体多硫化物，即使在70天的反应时间后，也能产生纯的聚亚硫醚。此外，过氧化氢在反应过程中产生了这两种物种，但在24 h后生成了完全转化的聚砜。通过使用温和的氧化剂，我们的方法控制了最终含硫聚合物中硫原子的氧化状态，防止了任何过氧化，从而确保了聚合物链的完整性和体系的胶体稳定性。通过对不同化学组成和结构的多硫化物的应用，验证了该方法的选择性、通用性和稳健性。这种方法表现出的普适性使其成为设计含硫聚合物和纳米颗粒的强大而简单的平台。
Polymers containing sulfur centers with high oxidation states in the main chain, polysulfoxide and polysulfone, display desirable properties such as thermomechanical and chemical stability. To circumvent their challenging direct synthesis, methods based on the oxidation of a parent polysulfide have been developed but are plagued by uncontrolled reactions, leading either to ill-defined mixtures of polysulfoxides and polysulfones or to polysulfones with reduced degrees of polymerization due to overoxidation of the polymer. We developed an alternative method to produce well-defined polysulfoxide and polysulfone in a waterborne colloidal emulsion using different oxidants to control the oxidation state of sulfur in the final materials. The direct oxidation of water-based polysulfide latexes avoided the use of volatile organic solvents and allowed for the control of the oxidation state of the sulfur atoms. Oxidation of parent polysulfides by tert-butyl hydroperoxide led to the production of pure polysulfoxides, even after 70 days of reaction time. Additionally, hydrogen peroxide produced both species through the course of the reaction but yielded fully converted polysulfones after 24 h. By employing mild oxidants, our approach controlled the oxidation state of the sulfur atoms in the final sulfur-containing polymer and prevented any overoxidation, thus ensuring the integrity of the polymer chains and colloidal stability of the system. We also verified the selectivity, versatility, and robustness of the method by applying it to polysulfides of different chemical compositions and structures. The universality demonstrated by this method makes it a powerful yet simple platform for the design of sulfur-containing polymers and nanoparticles.
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影响因子：
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