Wu Jianhui, Guan Xin, Wang Chunhua, Ngai To, Lin Wei
Department of Biomass and Leather Engineering, Key Laboratory of Leather Chemistry and Engineering of Ministry of Education, Sichuan University, Chengdu 610065, China; Department of Chemistry, The Chinese University of Hong Kong, Shatin, NT, Hong Kong.
Department of Chemistry, The Chinese University of Hong Kong, Shatin, NT, Hong Kong.
J Colloid Interface Sci. 2022 Mar 15;610:994-1004. doi: 10.1016/j.jcis.2021.11.156. Epub 2021 Nov 26.
Waterborne polyurethane (WPU) is a common colloidal dispersion that can aggregate in the aqueous phase to form nanoparticles with hydrophobic polyurethane chains as the core and hydrophilic ionic groups as the shell. Considering their structure and pH-responsive functional groups, WPU nanoparticles could be ideal particulate emulsifiers for preparing pH-responsive Pickering high internal phase emulsions (HIPEs).
A series of anionic WPU with different content of 2,2-bis(hydroxymethyl)propionic acid (DMPA) side chains were synthesized via a polyaddition reaction. The DMPA content, size, ζ-potential, and interfacial behaviors of WPU were then investigated. Furthermore, the effects of particle concentration, internal phase fraction (ϕ), oil type, and pH values on the Pickering HIPEs' morphology, stability, and rheological behaviors were systematically studied. Finally, we demonstrated the emulsification-demulsification process of WPU-stabilized Pickering HIPEs and discussed its mechanism.
Oil-in-water (O/W) Pickering HIPEs with tailored morphology and excellent pH-responsiveness were prepared from anionic WPU nanoparticles. The WPU concentration, ϕ, and oil type had a large impact on the formation and mean droplet size of the WPU-stabilized emulsions. Rheology analysis demonstrated that the strictly limited movement of droplets endowed the WPU-stabilized HIPEs with high stability, shear sensitivity, and excellent thixotropic recovery. By simply changing the aqueous-phase pH value, the WPU-stabilized HIPEs could undergo more than ten emulsification-demulsification cycles, as the physical and interfacial properties of WPU nanoparticles were pH-dependent. The excellent performance of the WPU-stabilized pH-responsive Pickering HIPEs exhibited their potential practical applications, such as for oil transportation and recovery, emulsion polymerization, and heterogeneous catalysis.
水性聚氨酯(WPU)是一种常见的胶体分散体,它可以在水相中聚集形成纳米颗粒,其核心为疏水性聚氨酯链,外壳为亲水性离子基团。考虑到其结构和pH响应官能团,WPU纳米颗粒可能是制备pH响应型皮克林高内相乳液(HIPEs)的理想颗粒乳化剂。
通过加成聚合反应合成了一系列具有不同含量2,2-双(羟甲基)丙酸(DMPA)侧链的阴离子型WPU。然后研究了WPU的DMPA含量、尺寸、ζ电位和界面行为。此外,系统研究了颗粒浓度、内相分数(ϕ)、油类型和pH值对皮克林HIPEs的形态、稳定性和流变行为的影响。最后,我们展示了WPU稳定的皮克林HIPEs的乳化-破乳过程并讨论了其机理。
由阴离子型WPU纳米颗粒制备了具有定制形态和优异pH响应性的水包油(O/W)皮克林HIPEs。WPU浓度、ϕ和油类型对WPU稳定乳液的形成和平均液滴尺寸有很大影响。流变学分析表明,液滴的严格受限运动赋予了WPU稳定的HIPEs高稳定性、剪切敏感性和优异的触变恢复性。通过简单改变水相pH值,WPU稳定的HIPEs可以经历十多次乳化-破乳循环,因为WPU纳米颗粒的物理和界面性质取决于pH值。WPU稳定的pH响应型皮克林HIPEs的优异性能展示了它们在诸如石油运输与回收、乳液聚合和多相催化等方面的潜在实际应用。